Chemical Photocatalysis 2nd Edition

Burkhard König
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Chemical
Photocatalysis

Edited by
Burkhard König

2nd Edition
Editor
Prof. Dr. Burkhard König
Universität Regensburg
Institut für Organische Chemie
Universitätsstr. 31
93053 Regensburg
burkhard.koenig@chemie.uni-regensburg.de

ISBN 978-3-11-057654-2
e-ISBN (PDF) 978-3-11-057676-4
e-ISBN (EPUB) 978-3-11-057664-1

Library of Congress Control Number: 2020931434

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2020 Walter de Gruyter GmbH, Berlin/Boston

Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck
Cover image: © Burkhard König

www.degruyter.com
Preface

The only sustainable energy source on earth is sunlight. Within one hour the cur-
rent annual energy demand of the world reaches the surface of earth as sunlight.
Many concepts to harvest, use and store this energy directly or from secondary pro-
cesses, such as wind or waves, are now under development to finally reduce our
dependency on fossil energy sources. While the conversion of light into electrical
energy has reached a high level of efficiency and is already at the stage of commer-
cial applications, the use of visible light to drive chemical reactions is much less
developed. This is surprising looking at the omnipresent biological photosynthesis,
which harvests and stores energy from sunlight in chemical products as the basis
for life on earth.
Light-induced reactions of molecules are the topic of a well established, classic
area of chemistry, which is called photochemistry. However, most of the work in
the past focused on direct excitation of molecules – and as most organic com-
pounds do not absorb in the visible part of the spectrum – the excitation requires
short wavelength (λ) ultraviolet irradiation, frequently in a region of λ = 250
−300 nm. On earth, solar irradiation is unsuited to induce these reactions because
its short wavelength contribution is luckily blocked by the ozone layer. The highest
intensity of light in the solar spectrum is found in the blue, green, and red region at
λ = 400−650 nm. To utilize this light energy for the conversion of molecules that do
not absorb above 300 nm, sensitizers or photocatalysts are required. In principle,
the concept of photocatalysis is well known, but less developed with respect to or-
ganic-chemical reactions: Visible light excites the sensitizer chromophore which
transfers energy or an electron to the substrate to be converted. The most prominent
example is the generation of reactive singlet oxygen from triplet oxygen by sensi-
tizers such as methylene blue or porphyrins. Although the energy content of visible
light is significantly lower compared to UV irradiation, it can still be sufficient to
overcome activation barriers, cleave weaker bonds and generate reactive intermedi-
ates for synthesis. The energy of green light at λ = 530 nm corresponds to 222 kJ/
mol, and blue light at λ = 400 nm to 300 kJ/mol.
In the last years the number of reports using visible (λ = 400−800 nm) and
UV A (λ = 320−400 nm) light in chemical synthesis has dramatically increased.
While one area of interest is the photocatalytic generation of dihydrogen as an en-
ergy source, other work focused on applications in synthesis mediating functional
group transformations or bond formations. High power LEDs have become cheaply
available as a perfect source of intense light in a defined wavelength range and
make, in combination with photomicroreactor and microflow technologies, explor-
atory chemistry with visible light technical simple and affordable. Selectivity issues
can now be addressed in a more sophisticated fashion. Catalytic cycles can be de-
signed, which guarentee an efficient turnover and high chemoselectivity. A number

https://doi.org/10.1515/9783110576764-202
VI Preface

of regio-, diastereo-, and even enantioselective reactions have become feasible in

recent years. The idea to use long wavelength light for chemical processes is by no
means new: More than 100 years ago Giacomo Ciamician promoted the use of visi-
ble light for chemical transformations as sustainable technology for the future. In
the context of post Industrial Revolution with steam engines and combustion cars
his ideas were not taken up widely, but now the time to consider photochemical
reactions for a sustainable future has come.
We summarize in this book the chemical and physical principles of photocatal-
ysis and discuss spectroscopic methods to determine the underlying reaction mech-
anisms. Recent examples of photocatalytic reactions are presented in various
chapters, classified by the type of photocatalysts (e. g. heterogeneous or metal com-
plex) or by the catalyzed reaction (photoorganoredox, arylation, oxidation, dihydro-
gen generation). The background information and the specific examples will give
the reader an overview of the state of the art in the field and its future perspectives.
The ongoing research presented in this book has been and continues to be sup-
ported by generous funding from the Deutsche Forschungsgemeinschaft, which es-
tablished in 2010 a graduate college on Chemical Photocatalysis (GRK 1626) at the
University of Regensburg (with collaborating groups in Munich and Erlangen).

Regensburg, Munich, August 2012

Burkhard König, Thorsten Bach
Preface to the second edition

Photochemistry and photocatalysis in organic synthesis have advanced at a fast

pace over the past five years. From a rediscovered methodology in chemistry, the
use of light in synthesis emerged in the first 15 years of this century into an enabling
technology improving many important reactions, such as cross-coupling reactions
or cycloaddition. In addition, new reaction modes were established, which were
previously difficult to achieve or even unknown, such as the formation of nitrogen
atom centered radicals of amides, alpha amino radical formation under mild condi-
tions or various C-H activation steps.
In the last years, nearly all areas of organic synthesis have seen new applica-
tions of light as a reagent to drive transformations. Photocatalysis evolved into a
standard technique in synthesis and is widely applied in academic and industry
laboratories around the world. First examples of photocatalytic production of mole-
cules on industrial scale have been reported and the number of such applications is
expected to rise. After the “gold rush” of fast discoveries of many photocatalytic re-
actions, detailed spectroscopic investigations start to unravel the mechanistic de-
tails. However, the field still has a long way to go to reach a comprehensive
understanding of reaction mechanisms at the molecular level.
The second edition of this book presents updated chapters and three new chap-
ters summarizing the background and recent achievements of the photochemistry
of radical ions, decarboxylative reactions and biomimetic photooxidations.
The research presented in this book has been supported by generous funding
from the Deutsche Forschungsgemeinschaft, which established from 2010 to 2019 a
graduate research training group on Chemical Photocatalysis (GRK 1626) at the
University of Regensburg in collaboration with groups at the universities of Munich
(TUM, LMU) and Leipzig.

Regensburg, Munich, December 2019

Burkhard König, Thorsten Bach

https://doi.org/10.1515/9783110576764-203
Contents
Preface V

Preface to the second edition VII

List of contributing authors XVII

Peter Schroll
1 Early pioneers of organic photochemistry 1
References 14

Bernhard Dick
2 Photophysics of photocatalysts 17
2.1 Setting the frame 19
2.2 The experimentalist’s perspective 23
2.3 The theoreticians’ perspective: A closer look 30
2.3.1 Transition probabilities 31
2.3.2 Orbitals 35
References 43

Burkhard König, Susanne Kümmel, Eva Svobodová and Radek Cibulka

3 Flavin photocatalysis 45
3.1 Introduction 45
3.1.1 General properties 46
3.2 Early examples of flavin photocatalysis 48
3.3 Flavin photocatalysis in synthesis application 52
3.4 Flavin-related compounds in photocatalysis 59
3.5 Isomerizations, cyclizations and cycloeliminations 61
3.6 Photooxidations via singlet oxygen mechanism 63
3.7 Conclusion 64
References 65

Andreas Bauer and Rafael Alonso Ruiz

4 Templated enantioselective photocatalysis 73
4.1 Introduction 73
4.2 Early studies. Paternò–Büchi cycloadditions of a chiral aromatic
aldehyde and cyclic enamines 75
4.3 Enantioselective Norrish–Yang cyclization reaction of prochiral
imidazolidinones 76
4.4 Enantioselective photochemical [4 + 4]-cycloadditions and
electrocyclic [4π]-ring closure of 2-pyridones 77
X Contents

4.5 Enantioselective [6π]-photocyclization of acrylanilides 78

4.6 Enantioselective Diels–Alder reaction of a photochemically
generated ortho-quinodimethane 79
4.7 Formal [3 + 2]-photocycloadditions of 2-substituted
naphthoquinones 80
4.8 Intramolecular [2 + 2]-photocycloadditions of substituted 5,6-
dihydro-1H-pyridin-2-ones 80
4.9 Enantioselective radical cyclizations 81
4.9.1 Reductive radical cyclization reactions of 3-(ω-iodoalkylidene)-
piperidin-2-ones 81
4.9.2 Reductive radical cyclization of 3-(3-iodopropoxy)propenoic acid
derivatives 82
4.9.3 Radical cyclization reactions of 4-substituted quinolones 82
4.10 [2 + 2]-photocycloaddition reactions of isoquinolones 83
4.11 [2 + 2]-photocycloaddition reactions of substituted
quinolones 85
4.11.1 Intermolecular [2 + 2]-photocycloaddition reactions of
quinolones 85
4.11.2 Inter- and intramolecular [2 + 2]-photocycloadditions of 4-(2′-
aminoethyl)quinolones 86
4.11.3 Intramolecular [2 + 2]-photocycloadditions of 4-(ω-alkenyloxy)-
quinol-2-ones 87
4.12 Light-induced enantioselective catalysis 88
4.12.1 Enantioselective type II photooygenations of 2-pyridones 90
4.12.2 Enantioselective addition of α-amino radicals to 3-alkylidene
indolin-2-ones 91
4.12.3 Catalyzed enantioselective photo-induced electron transfer
reactions 92
4.12.4 Xanthone-catalyzed enantioselective [2 + 2]-photocycloadditions
of quinolones 92
4.12.5 Intermolecular enantioselective [2 + 2]-photocycloadditions of
pyridones 95
4.12.6 Enantioselective [2 + 2]-photocycloadditions using visible light 95
4.13 Conclusion 97
References 97

Arthur Kuhlmann, Sergej Hermann, Michael Weinberger, Alexander Penner

and Hans-Achim Wagenknecht
5 Photocatalysis with nucleic acids and peptides 103
5.1 Introduction 103
5.2 DNA-assisted enantioselective reactions 104
5.2.1 Photocatalytically active DNA (PhotoDNAzymes) 106
 Contents XI

5.2.2 Benzophenone as photosensitizers for PhotoDNAzymes 106

5.3 Small peptides as organocatalysts 112
5.3.1 Development of peptides for photocatalytic addition to
styrenes 114
5.4 Conclusion 117
References 118

Johanna Schwarz
6 Photocatalytic decarboxylations 123
6.1 Introduction 123
6.2 Decarboxylative reactions 126
3
6.2.1 Reactions via sp -hybridized radicals from alkyl carboxylic
acids 126
6.2.2 Reactions via sp2-hybridized radicals 135
6.3 Conclusion 142
References 143

Magnus Rüping, Rene M. Königs and Iuliana Atodiresei

7 Photoredox catalyzed α-functionalization of amines – visible light
mediated carbon-carbon and carbon-hetero bond forming reactions 147
7.1 Introduction 147
7.2 Aza-Henry reaction 151
7.3 Addition of malonates 154
7.4 Mannich reaction 155
7.5 Allylation 156
7.6 Cyanation of tertiary amines 157
7.7 Alkynylation 157
7.8 [3+2] cycloaddition reaction 158
7.9 Acylation 159
7.10 C-heteroatom (C–P, C–O, C–N) bond formation 159
7.11 Conclusion 161
References 161

Filip Teplý
8 Visible-light photoredox catalysis with [Ru(bpy)3]2+: General
principles and the twentieth-century roots 163
8.1 Introduction 163
8.2 [Ru(bpy)3]2+ and its photoredox properties 164
8.3 Application of [Ru(bpy)3]2+ as catalyst in the twentieth
century 166
8.4 Conclusions 183
References 184
XII Contents

Lukas Traub and Oliver Reiser

9 Homogeneous visible light mediated transition metal catalysis other
than Ruthenium and Iridium 193
9.1 Introduction 193
9.2 Copper in visible light catalysis 194
9.3 Chromium in visible light catalysis 201
9.4 Iron in visible light catalysis 203
9.5 Nickel in visible light catalysis 207
9.6 Zirconium in visible light catalysis 207
9.7 Molybdenum in visible light catalysis 209
9.8 Cerium in visible light catalysis 210
9.9 Rhenium and platinum in visible light catalysis 212
9.10 Uranium in visible light catalysis 214
9.11 Summary 215
References 216

Bernd Mühldorf, Ulrich Lennert and Robert Wolf

10 Coupling photoredox and biomimetic catalysis for the visible-light-
driven oxygenation of organic compounds 223
10.1 Introduction 223
10.2 Combining photoredox catalysis with heme-type catalysts 225
10.3 Combining photoredox catalysis with biomimetic non-heme iron
catalysts 226
10.4 Coupled photoredox catalysts based on copper 229
10.5 Di- and trinuclear ruthenium dyads for oxygenation 231
10.6 Biocatalytic oxygenation 234
10.7 Summary 237
References 239

Kirsten Zeitler and Matthias Neumann

11 Synergistic visible light photoredox catalysis 245
11.1 Introduction 245
11.2 Stabilized iminium ions 248
11.2.1 Secondary amine catalyzed Mannich reactions 249
11.2.2 Coinage metal catalyzed alkynylation reactions 252
11.2.3 NHC catalyzed acylations 254
11.3 Electrophilic carbon centered radicals 256
11.3.1 Secondary amine catalyzed α-alkylation of aldehydes 256
11.3.2 Palladium-catalyzed C-H arylation 262
11.3.3 Copper-catalyzed trifluoromethylation of aryl boronic
acids 264
 Contents XIII

11.3.4 Gold-catalyzed intra- and intermolecular arylative

transformationsof alkenes and alkynes 265
11.4 Nucleophilic carbon centered radicals 267
11.4.1 Carbonyl radical anion (ketyl radical) and related species 267
11.4.2 α-Amino alkyl radicals 270
11.4.3 β-Enaminyl radicals 272
11.4.4 Alkyl radicals in Ni/photoredox dual catalytic cross coupling
reactions 272
11.5 Conclusions and Future Outlook 275
References 276

Indrajit Ghosh
12 Excited radical anions and excited anions in visible light photoredox
catalysis 285
12.1 Introduction 285
12.2 Radical anions as visible light absorbing photosensitizers 286
12.2.1 Perylene diimide radical anion 286
12.2.2 Rhodamine 6G (Rh-6G) radical anion 290
12.2.3 9,10-Dicyanoanthracene (DCA) radical anion 294
12.2.4 Anthraquinone radical and semiquinone anions 295
12.3 Excited state anions in visible light photoredox catalysis 295
12.4 The ground state PAH’s radical anions in visible light photoredox
catalysis 296
12.5 Conclusion 297
References 298

Sven Rau, Michael G. Pfeffer and Robert Staehle

13 Metal complexes for photohydrogenation and hydrogen
evolution 301
13.1 Analysis of construction components of artificial photocatalytic
systems 303
13.1.1 Chromophore 303
13.1.2 Electron relay 304
13.1.3 Redox equivalents 304
13.1.4 Reduction catalysts 304
13.1.5 Intramolecular hydrogen evolving photocatalysts 305
13.1.6 Oxidation catalysts 306
13.1.7 Intramolecular oxidation catalysts 307
13.1.8 Comparison of inter- and intramolecular photocatalysis 307
13.2 Intramolecular photocatalysts for hydrogen production and
hydrogenation 309
XIV Contents

13.2.1 Hydrogen production 310

13.2.2 Photohydrogenation 312
13.2.3 Photophysics 313
13.2.4 Ru(tpphz)Pd-type catalysts as photochemical molecular devices
(PMD) 318
13.3 Conclusion 320
References 321

Arno Pfitzner, Stephan Dankesreiter, Anna Eisenhofer and Maria

Cherevatskaya
14 Heterogeneous semiconductor photocatalysis 327
14.1 Inorganic semiconductors 327
14.1.1 General features of a photocatalyst 327
14.1.2 How to tune a photocatalyst 333
14.1.3 Selected examples of photocatalysts and their application to
organic synthesis 337
14.2 Organic semiconductors 346
14.2.1 Basic properties of organic semiconductors 347
14.2.2 Application of conjugated polymers in photocatalysis 348
References 355

Carsten Streb, Katharina Kastner and Johannes Tucher

15 Polyoxometalates in photocatalysis 363
15.1 Introduction 363
15.1.1 Polyoxometalates – molecular metal oxide clusters 363
15.1.2 Concepts in polyoxometalate photochemistry 364
15.1.3 The basics of POM photochemistry 366
15.1.4 Traditional photooxidation of organic substrates 366
15.2 Recent developments in POM photochemistry 366
15.2.1 Water oxidation by Ru- and Co-polyoxometalates 367
15.2.2 Polyoxoniobate water oxidation 367
15.2.3 Water oxidation by Dawson anions in ionic liquids 369
15.2.4 Photoreductive CO2-activation 369
15.2.5 Photoreductive H2 generation 370
15.3 Optimizing photocatalytic performance of polyoxometalates 371
15.3.1 Structurally adaptive systems 371
15.3.2 Optimized photoactivity by metal substitution 372
15.3.3 Inspiration from the solid-state world 373
15.4 Conclusion 374
References 375
 Contents XV

Thomas Merz, Genaro Bierhance, Ernst-Christian Flach, Daniel Kats, Denis

Usvyat and Martin Schütz
16 Description of excited states in photochemistry with theoretical
methods 379
16.1 Introduction 379
16.2 The concept of PESs 381
16.3 Computational methods for excited states 385
16.3.1 QM methods 385
16.3.2 Solvent description via the QM/MM approach 387
16.4 Procedure 391
16.5 Examples 392
16.6 Roseoflavin 394
16.7 Benzophenone in dinucleotides 399
16.8 Photoinduced ring closure in DAE 405
16.9 Conclusion 408
References 409

Bernhard Dick, Uwe Kensy, and Roger Jan Kuttaand

17 Transient absorption with a streak camera 415
17.1 Introduction 415
17.2 Experimental setup 418
17.3 Data analysis 420
17.3.1 SVD and rank analysis 421
17.3.2 Global lifetime analysis 422
17.3.3 Eliminating invalid data 423
17.3.4 Maximum entropy analysis 424
17.4 Performance 428
17.4.1 RFTA alone 428
17.4.2 Photooxidation of MBA with RFTA 432
17.5 Discussion 434
17.6 Conclusion 437
References 438

Eberhard Riedle and Matthias Wenninger

18 Time resolved spectroscopy in photocatalysis 443
18.1 UV/Vis absorption spectroscopy: More than just ε! 443
18.2 Time-Resolved spectroscopic methods from fs to µs to elucidate
photocatalytic processes 447
18.2.1 Transient absorption spectroscopy: Signals, time scales, and
data processing 447
18.2.2 Spectroscopy on the fs to ps time scale 450
18.2.3 Spectroscopy on the ns to µs time scale 455
XVI Contents

18.2.4 Rate models and the determination of the species associated

spectra of the intermediate states 461
18.3 Diffusion limited reactions 469
18.3.1 Diffusion limited excited state quenching with time dependent
reaction rate 469
18.3.2 Application of the diffusion fit function to experimental data 475
18.4 Costs of photocatalysis: The reaction quantum yield 481
18.4.1 Requirements for an accurate definition of the quantum yield 481
18.4.2 Determination of the quantity of excited molecules in transient
absorption measurements 486
18.4.3 Example of the spectroscopic determination of reaction quantum
yields: Flavin photocatalysis 488
18.5 From light absorption to chemistry: Sensitizing mechanisms in
homogeneous photocatalysis 493
18.5.1 Sensitization by excitation energy transfer 493
18.5.2 Photoredox catalysis: Requirements on catalyst and
substrate 494
18.6 Epilogue 498
References 500

Index 503
List of contributing authors

Rafael Alonso Ruiz Sergej Hermann

Valencia Karlsruher Institut für Technologie - Institut
Spain für Organische Chemie
rafaelalru@gmail.com Germany

Andreas Bauer Katharina Kastner

Technical University of Munich Ulm University – Inorganic Chemistry I
Department of Chemistry Germany
Germany katharina.kastner@uni-ulm.de
andreas.bauer@tum.de
Daniel Kats
Genaro Bierhance Max-Planck-Institut für Festkörperforschung
Fritz-Haber-Institut der Max-Planck- Stuttgart
Gesellschaft Germany
Abt. Physikalische Chemie d.kats@fkf.mpg.de
Berlin
Germany Burkhard König
bierhance@fhi-berlin.mpg.de Universität Regensburg
Fakultat für Chemie und Pharmazie
Radek Cibulka Germany
University of Chemistry and Technology, Prague burkhard.koenig@chemie.uni-regensburg.de
Department of Organic Chemistry
Czech Republic Rene Königs
cibulkar@vscht.cz Institut für Organische Chemie
RWTH Aachen
Bernhard Dick Germany
Universität Regensburg rene.koenigs@rwth-aachen.de
Institut für Physikalische und Theoretische
Chemie Regensburg Arthur Kuhlmann
Germany Karlsruher Institut für Technologie - Institut
bernhard.dick@ur.de für Organische Chemie
Germany
Ernst-Christian Flach arthur.kuhlmann@kit.edu
Humboldt-Universitat zu Berlin
Mathematisch Naturwissenschaftliche Fakultät Susanne Kümmel
Institut für Chemie, Abt. Theoretische Universität Regensburg
Chemie Fakultat für Chemie und Pharmazie
Germany Germany
echristianflach@web.de susanne_kuemmel@gmx.de

Indrajit Ghosh Ulrich Lennert

Universität Regensburg Universität Regensburg
Germany Institut für Anorganische Chemie
Indrajit1.Ghosh@chemie.uni-regensburg.de Germany

https://doi.org/10.1515/9783110576764-205
XVIII List of contributing authors

Thomas Merz Peter Schroll

Universitat Regensburg Universität Regensburg
Fakultät fur Chemie und Pharmazie Fakultät für Chemie und Pharmazie
Ringgold standard institution Institut für Organische Chemie
Germany Germany

Bernd Mühldorf Martin Schütz

Universität Regensburg Humboldt-Universität zu Berlin
Institut für Anorganische Chemie Mathematisch Naturwissenschaftliche
Germany Fakultät
Institut für Chemie, Abt. Theoretische
Matthias Neumann Chemie
Universität Regensburg Germany
Germany
dr.m.neumann@gmx.net Johanna Schwarz
Universität Regensburg
Alexander Penner Fakultät für Chemie und Pharmazie
Karlsruher Institut für Technologie Germany
Germany
Carsten Streb
Arno Pfitzner Ulm University - Inorganic Chemistry I
Institut für Anorganische Chemie Germany
Universität Regensburg carsten.streb@uni-ulm.de
Germany
arno.pfitzner@ur.de Eva Svobodová
University of Chemistry and Technology,
Sven Rau Prague
Anorganische Chemie I Department of Organic Chemistry
Universiät Ulm Czech Republic
Germany svobodoe@vscht.cz
sven.rau@uni-ulm.de
Johannes Taucher
Oliver Reiser Ulm University – Inorganic Chemistry I
Universität Regensburg - Organische Chemie Germany
Germany johannes.tucher@uni-ulm.de
oliver.reiser@ur.de
Filip Teply
Eberhard Riedle Institute of Organic Chemistry and
Lehrstuhl für BioMolekulare Optik Biochemistry of the Czech Academy of
Ludwig-Maximilians-Universität Sciences
Germany Prague
Eberhard.Riedle@Physik.uni-muenchen.de Czech Republic

Magnus Rueping Lukas Traub

KAUST Catalysis Center Universität Regensburg - Organische
KAUST Chemie
Thuwal Germany
Saudi Arabia Lukas.Traub@chemie.uni-regensburg.de
Magnus.Rueping@Kaust.edu.sa
 List of contributing authors XIX

Denis Usvyat Michael Weinberger

Humboldt-Universitat zu Berlin Karlsruher Institut für Technologie
Mathematisch Naturwissenschaftliche Germany
Fakultat
Institut für Chemie, Abt. Theoretische Robert Wolf
Chemie Universität Regensburg
Germany Institut für Anorganische Chemie
denis.usvyat@chemie.hu-berlin.de Germany
Robert.Wolf@chemie.uni-regensburg.de
Hans-Achim Wagenknecht
Karlsruher Institut für Technologie Kirsten Zeitler
Institut für Organische Chemie Universität Leipzig - Institut für Organische
Germany Chemie
Wagenknecht@kit.edu Germany
kirsten.zeitler@uni-leipzig.de
Peter Schroll
1 Early pioneers of organic photochemistry

Abstract: A summary of the beginnings of organic photochemistry from a synthetic

point of view is presented. Accidentally discovered reactions driven by light as well
as systematic studies on the behavior of light toward matter leading to the develop-
ment of a new branch of chemistry are discussed.

“When oil will have been all burned in our prodigal industries, it may become nec-
essary, even on social grounds, to come to exploit solar energy.” [1] This foresight-
ful statement fits perfectly into modern debates at the beginning of the twenty-first
century about the necessity of using renewable energies, but is in fact more than
one hundred years old, written by Giacomo Ciamician, an early pioneer of organic
photochemistry. He was a visionary chemist who was invaluable in developing pho-
tochemistry, an upcoming science at the beginning of the twentieth century. Apart
from his credits to discover several new photochemical reactions, he was interested
in using these reactions on an industrial scale. Nevertheless, chemical transforma-
tions under the influence of light were known long before. In 1790, Joseph
Priestley (1733–1800) exposed partially filled vials of “spirit of nitre” (nitric acid)
to sunlight and observed a reddish color, which was attributed to the formation of
nitrogen dioxide (Figure 1.1). This first photochemical reaction in the gas phase
marks the beginning of photochemistry [2]. Moreover, Priestley is given credit for
discovering basic principles of photosynthesis, the most important photochemical
process for living organisms on earth. He “fully ascertained the influence of light in
the production of dephlogisticated air (oxygen) in water by means of a green sub-
stance,” which was identified as tiny plants [2, 3]. After Nicholas Theodore de
Saussure (1767–1845) had shown in 1804 that the influence of light causes plants
to consume water and carbon dioxide and to generate oxygen, a fundamental un-
derstanding of the process of photosynthesis in green plants had been discovered
[2, 4].
The English chemist Sir Humphry Davy (1778–1829) used sunlight to produce
phosgene out of a mixture of chlorine and carbon dioxide in 1812 [5]. Moreover, dur-
ing his studies of halogens and their salts he discovered the light sensitivity of sil-
ver iodine, which created the basis for the process of photography. For decades,
photography was the most important application of photochemical processes.
As early as 1831, Johann Wolfgang Döbereiner (1780–1849) reported the
light-induced reduction of metal ions by oxalic acid [2, 6]. In the case of an aqueous
solution of oxalic acid and iron(III) oxide irradiated by sunlight, he obtained carbon
dioxide and humboldtite, a basic iron(II) oxide. Similarly, he reduced salts of plati-
num, silver and iridium. In each case, the result was checked by control experi-
ments in the dark. Unfortunately, he was not able to report the first photoreaction

https://doi.org/10.1515/9783110576764-001
2 1 Early pioneers of organic photochemistry

Figure 1.1: Joseph Priestley (1733–1800), English

philosopher, chemist and physicist.

of a ruthenium compound, whose complexes today serve as powerful photocata-

lysts, since ruthenium was discovered 13 years later in 1844.
The following decades were characterized by accidental discoveries of photo-
chemical reactions. Several researchers contributed to the new field of photochemistry
by discovering single reactions. Among the first reactions were [2 + 2]-cycloadditions,
geometric isomerizations, light-induced halogenations, photoreductions of carbonyl
compounds and photodimerizations.
Carl Julius Fritzsche (1808–1871) observed the light sensitivity of anthracene
in 1867: “When a cold, saturated solution [of anthracene] is exposed to sunlight,
microscopic crystals begin to precipitate.” [7] However, it took another 25 years to
recognize the photoproduct, being the dimer of anthracene, as a result of a [4 + 4]-
cycloaddition [8]. In this case, the photoreaction was discovered due to the fact that
the photoproduct was less soluble than the starting material.
In 1877, Carl Theodor Liebermann (1842–1914), a German chemist working in
Berlin, observed the conversion of yellow crystals of thymoquinone (2-isopropyl-5-
methylbenzoquinone) producing a white photoproduct under irradiation with sun-
light (Figure 1.2). This was the first example of a [2 + 2]-cycloaddition [9]. It is worth
mentioning that he was the first to test artificial light sources since early photo-
chemists used sunlight as the only and most important source of radiation at that
time [10]. Liebermann is today known as a pioneer of solid-state photochemistry
due to his examinations concerning the dimerization of quinones and styrene deriv-
atives [11]. As far as the latter are concerned, Bertram and Kürsten, two chemists
working in industry, were a few months faster in publishing the light-mediated di-
merization of cinnamic acid and are therefore given credit for the discovery of the
dimerization of styrene derivatives [12]. However, Liebermann was the most impor-
tant photochemist of the nineteenth century.
 1 Early pioneers of organic photochemistry 3

Figure 1.2: Carl Theodor Liebermann (1842–1914), a

pioneer of solid-state photochemistry.

The first geometric isomerization of olefins was reported by William Henry

Perkin (1838–1907) in 1881 (Figure 1.3). He irradiated 2-alkoxy-cinnamic acid and ob-
tained the “β-isomer.” [13] Liebermann found out that iodine accelerates the cis-trans
isomerization of aromatic unsaturated acids such as δ-phenylpentadienoic acid [10].
Johannes Wislicenus (1835–1902) was able to extend the method to nonaromatic
systems. Among others, when he irradiated maleic acid in an aqueous solution of
bromine, fumaric acid was obtained [2, 14].

Figure 1.3: William Henry Perkin examined the first

light-induced geometric isomerizations.
4 1 Early pioneers of organic photochemistry

Halogens also played an important role in photochemical experiments of

Julian Schramm (1852–1926) in Lemberg. Between 1884 and 1888 he studied the
light-induced bromination of alkylbenzenes and found out “that light and darkness
work in the same way as elevated and low temperatures, respectively.” [15] At that
time it was known that the selectivity of a halogenation reaction is temperature-de-
pendent: at low temperatures, the aromatic ring is halogenated while at elevated
temperatures a substitution reaction occurs at the alkyl side chain. The new aspect
of his work was the finding that the halogenation reaction can be carried out with
light and that the selectivity can be controlled using sunlight irradiation or dark-
ness. Moreover, Schramm was the first to realize the potential of this type of reac-
tion for industrial application. Today, photochlorination is an important tool in
industrial synthesis.
An impressive example of an accidental discovery of a new reaction is given by
Heinrich Klinger (1853–1945). During his attempts to convert benzil to isobenzil in
an aqueous solution of ether, he observed the unexpected formation of crystals. A
close examination showed that the outcome of the reaction was not reproducible.
Looking for the unknown parameter, he realized that “some of the tubes were exposed
to sunlight in the morning hours.” [16] The crystals were identified as a molecular
complex of benzil and benzoin. Hence, in 1886, Klinger had observed the first light-
mediated reduction of a keto group to the corresponding alcohol. A subsequent study
of different ketones and the replacement of ether by an aldehyde led to interesting
results. The intermolecular photoreaction of benzoquinone with benzaldehyde, for ex-
ample, resulted in the formation of a new carbon-carbon bond in the photoproduct
2,5-dihydroxybenzophenone [17]. He observed a “synthetic effect of light” which he
compared to photosynthesis in living plants [18]. This reaction is considered to be the
first photoreaction for synthetic purposes.
After all these preliminary reactions had been reported and the knowledge
about photochemical reactions had increased, the time was ready for a systematic
study of light-driven reactions. Italy, as it turned out, would become a center of re-
search for photochemical reactions. The development of photochemistry in Italy is
closely related with the photoreaction of santonin 1 (Figure 1.6). This is the longest
known photoreaction of an organic compound. Santonin was formerly used as an
anthelmintic drug, but is today replaced by less toxic agents. In 1834, Hermann
Trommsdorff (1811–1884), a pharmacist in Erfurt (Germany), observed a color
change of white santonin crystals to yellow ones followed by a crystal burst after
exposure to sunlight [19]. Moreover, he examined the wavelength dependency of
the reaction by means of a prism. He found out that the yellow color of the crystals
appears after irradiation with direct sunlight as well as with violet and blue rays,
but not with green, yellow or red beams. Looking back, this was a remarkable result
for the first half of the nineteenth century, since not much was known about the
nature of light at that time. Later scientists continued at this stage. Perkin and
Klinger used colored solutions such as sulfate of quinine, cuprous ammonium
 1 Early pioneers of organic photochemistry 5

sulfate and potassium dichromate as filters. Both researchers attributed the photo-
chemical reactivity of their systems to the blue, violet and ultraviolet rays. Further
investigations of Trommsdorff led to the result that santonin and its photoproduct
were isomers. However, both structures could not be determined exactly with the
methods of that time. The problem remained unsolved.
Several years later, Fausto Alessandro Sestini (1839–1904), an Italian chemist
working in Rome, was faced with the problem of santonin and its photoreaction
(Figure 1.4). He identified the photoproduct as photosantonic acid. Sestini is also
considered to be the founder of photochemistry in Italy. Cooperating with
Stanislao Cannizzaro (1826–1910) in Rome (Figure 1.5), with Sestini introducing
Cannizzaro to photochemistry, both scientists continued to work together on this
topic [20].

Figure 1.4: Fausto Alessandro Sestini, the originator of

photochemistry in Italy, worked on the elucidation of the
photorearrangement of santonin.

In almost 20 years of examination of the santonin photoreaction, Cannizzaro dis-

covered an additional intermediate of the reaction which they called isophotosan-
tonic acid [21, 22]. The final structure of photosantonic acid 5 was not described
correctly until 1958, that is, 124 years after Trommsdorff first observed this photore-
action [23, 24]. Today we know that santonin 1 and photosantonic acid 5 have differ-
ent crystal structures. This is the explanation for the observation that sunlight
causes crystals of santonin to burst. The pathway for the rearrangement is given in
Figure 1.6.
In his laboratory in Rome, Cannizzaro introduced Giacomo Ciamician and Paul
Silber to photochemistry, two researchers, who had great influence in the develop-
ment of this new branch of chemistry. Giacomo Ciamician (1857–1922) was an
Italian chemist of Armenian descent who joined the Cannizzaro group in 1881 where
6 1 Early pioneers of organic photochemistry

Figure 1.5: Stanislao Cannizzaro introduced Ciamician and

Silber to photochemistry.

Santonin Rearrangement

O
sunlight sunlight
O O
O O O
O O O
santonin lumisantonin 3
1 2

sunlight H 2O

C HOOC
O
O O
O O
4 photosantonic acid
5

Figure 1.6: Photorearrangement of santonin to photosantonic acid.

he, too, was faced with the problem of the santonin reaction (Figure 1.7). In 1885, he
started the first photochemical examinations and soon the German Paul Silber
(1851–1932) joined his projects [25]. They discovered the photoreduction of nitroben-
zene to aniline and 2-methylquinoline in an alcoholic solution and found out that a
solution of benzoquinone in ethanol is converted to hydroquinone and acetaldehyde
after five months of solar irradiation [26]. Although the work had been carried out
independently from Klinger’s photoreduction of ketones in Bonn (Germany), the lat-
ter was several months faster in publishing his results and claimed this field for his
own research, which was possible in the nineteenth century. Thus, Ciamician’s and
Silber’s first excursion in the field of organic photochemistry had come to a sudden
 1 Early pioneers of organic photochemistry 7

Figure 1.7: Giacomo Ciamician’s (left) and Paul Sailber’s (right) work surpassed any previous effort
in photochemistry.

end. They did not continue their work in photochemistry until the year 1900.
Ciamician moved to Padua in 1887 and then to Bologna in 1889 where he was accom-
panied by Paul Silber who became a co-worker for the next 25 years, until World War
I ended their partnership [27]. The skills of both researchers, with “Ciamician as the
genial and critical research director” and “Silber as the skilled and patient experi-
menter”, being able to isolate and identify even labile photoproducts, made this col-
laboration “a profitable partnership” [28]. Restarting in 1900, Ciamician and Silber
conducted the first systematic study of the behavior of organic compounds toward
light. This was the most complete study of the effect of light at that time. Ciamician
was known for his enthusiastic dedication to teaching characterized by an interdisci-
plinary character [29]. In a lecture before the French Chemical Society in 1908, he
summarized and classified the photoreactions discovered by him and other research-
ers [1]. Among the reported reactions were photochemical reactions of carbonyl
groups such as oxidation, reduction and hydrogen transfer as well as α- and β-cleav-
age, reduction of nitro compounds, condensation reactions such as cycloaddition, di-
merization or photopinacolization forming a new carbon-carbon bond, autoxidation,
and geometric isomerization of several unsaturated compounds [27, 30].
Ciamician’s earliest photochemical experiment, the photochemistry of quinones,
is a light-mediated redox reaction. An alcoholic solution of 1,4-benzoquinone was
converted to hydroquinone and acetaldehyde under irradiation with sunlight. Both
processes, the oxidation as well as the reduction, were useful reactions. As far as the
oxidative side is concerned, a mild and selective oxidation of primary alcohols to al-
dehydes was found. This is particularly interesting since not too many synthetic tools
are available for such a transformation. One might think of the Swern oxidation or
the use of toxic chromium reagents, for example. With sunlight, the oxidation takes
place under very mild conditions. Secondary alcohols were found to be oxidized to
8 1 Early pioneers of organic photochemistry

ketones, e.g. isopropanol to acetone. Furthermore, polyalcohols were oxidized to sug-

ars, as shown by the reactions of glycerol to glyceraldehyde, erythrol 6 to erythrose 7,
and mannitol to mannose (Figure 1.8) [31–33]. All these reactions benefit from the
photoactivated oxidizing ability of 1,4-benzoquinone.
Taking the reducing side, not only was benzoquinone transformed to hydroqui-
none, but also aromatic ketones were found to undergo photopinacolization, since aro-
matic ketones underwent clean bimolecular reduction to pinacols in the presence of an
alcohol as a reducing agent. Alloxane 8 was converted to alloxantin 9 (Figure 1.8) and
aldehydes gave hydrobenzoins. These reactions were of preparative interest. The mech-
anistic background is the high reactivity of the triplet state of carbonyls and other nπ*
states with regard to fast hydrogen abstraction generating C-centered radicals.
In a similar way, the reaction was used for the light-driven reductive alkylation
of ketones. Aromatic ketones such as benzophenone in the presence of benzylalco-
hol gave the alkylated product 10 (Figure 1.8). The reaction was considered to be
similar to the aldol reaction.
Another group of photooxidants is that of nitroaromatics. They were reduced to
the corresponding anilines upon irradiation in alcohols [34, 35]. Of particular im-
portance was the intramolecular reaction of ortho-nitrobenzaldehyde 11 to give
ortho-nitrosobenzoic acid 12 (Figure 1.8). This process was by far faster than other
conversions, which were typically in the time scale of weeks or months [36].
Nowadays, intramolecular hydrogen abstraction by a nitro group is widely used in
terms of the ortho-nitrobenzyl moiety as a photoremovable protecting group.
Besides oxidation reactions with benzoquinone or nitro compounds as oxi-
dants, Ciamician and Silber discovered oxidation reactions involving molecular ox-
ygen. Stilbene was converted to benzaldehyde in the presence of light and oxygen.
The mechanism was explained by addition of the oxygen molecule to the double
bond of stilbene forming a dioxetane intermediate followed by cleavage of the four-
membered ring.
Ketones such as acetone were oxidatively cleaved giving acetic and formic acid
under aerobic conditions. Furthermore, fragmentation reactions were found to occur
in aqueous media. Irradiation of acetone gave acetic acid and methane – a formal
hydrolysis of the carbon-carbon bond in α-position to the carbonyl group – as a result
of α-cleavage. This reaction is today known as the Norrish Type I reaction. The name
was established after detailed examinations in the gas phase by the English chemist
Ronald George Wreyford Norrish (1897–1978) in the 1930s [37, 38]. Cyclic ketones
were noticed to give two different products: open-chain saturated acids and unsatu-
rated aldehydes. For example, the cleavage of cyclohexanone yielded hexanoic acid
13 and ω-hexenal 14. The latter product was obtained by a Norrish Type II reaction,
as it was called later (Figure 1.8). The identification of all products must be attributed
to the extraordinary experimental skills of the scientists since it was very difficult to
characterize aliphatic aldehydes at that time.
 1 Early pioneers of organic photochemistry 9

Ciamician’s Types of Photoreactions

Selective oxidation of alcohols

OH OH
sunlight
HO HO
OH O
OH O OH
erythrol erythrose
6 O 7

Photo-pinacolization
O O O
NH sunlight HN OH NH
2 O O O O
NH HN HO NH
O O O
alloxane alloxantin
8 9

Reductive alkylation of ketones

O sunlight OH OH
Ph Ph Ph
HO Ph

10
Nitroaromatics as photooxidants
O O
sunlight
H OH

NO2 NO
11 12

α-Cleavage
O
C H2O COOH
O O
sunlight
13
Norrish Type l O

H
Norrish Type ll

14
Intramolecular [2+2] cycloaddition

* sunlight
O
EtOH, H2O

carvone carvonecamphor
15 16

Figure 1.8: Types of photochemical reactions discovered by Ciamician and Silber.

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 (Larger)

Map of Plymouth Harbor, Massachusetts, adapted from a

modern chart for comparison with Champlain’s map of Port St.
Louis, to which it is adjusted as nearly as possible in scale,
extent, and meridian
Reproduced from the Champlain Society edition of The Works of Samuel de
Champlain, plate LXXIV. The compass is Champlain’s, which is supposed to
be set to the magnetic meridian, but the true north is shown by the arrow.

Champlain’s Plymouth visit occurred in 1605, two years after

Pring’s expedition. He had spent several days in Gloucester Harbor
and a night in Boston Harbor, where he had watched the building of
a dugout canoe by the Indians. Coming down the South Shore, his
bark grounded on one of the numerous ledges that dot that portion of
Massachusetts Bay. “If we had not speedily got it off, it would have
overturned in the sea, since the tide was falling all around, and there
were five or six fathoms of water. But God preserved us and we
anchored” near a cape, which perhaps was Brant Rock. “There
came to us fifteen or sixteen canoes of savages. In some of them
there were fifteen or sixteen, who began to manifest great signs of
joy, and made various harangues, which we could not in the least
understand. Sieur de Monts sent three or four in our canoe, not only
to get water but to see their chief, whose name was Honabetha.—
Those whom we had sent to them brought us some little squashes
as big as the fist which we ate as a salad like cucumbers, and which
we found very good—We saw here a great many little houses
scattered over the fields where they plant their Indian corn.”
The expedition now sailed southward into Plymouth Harbor. “The
next day [July 18] we doubled Cap St. Louis, so named by Sieur de
Monts, a land rather low, and in latitude 42° 45’. The same day we
sailed two leagues along a sandy coast as we passed along which
we saw a great many cabins and gardens. The wind being contrary,
we entered a little bay [Plymouth] to await a time favorable for
proceeding. There came to us two or three canoes, which had just
been fishing for cod and other fish, which are found there in large
numbers. These they catch with hooks made of a piece of wood, to
which they attach a bone in the shape of a spear, and fasten it very
securely. The whole thing has a fang-shape, and the line attached to
it is made out of the bark of a tree. They gave me one of their hooks,
which I took as a curiosity. In it the bone was fastened on by hemp,
like that in France, as it seemed to me. And they told me that they
gathered this plant without being obliged to cultivate it; and indicated
that it grew to the height of four or five feet. This canoe went back on
shore to give notice to their fellow inhabitants, who caused columns
of smoke to rise on our account. We saw eighteen or twenty
savages, who came to the shore and began to dance.” Was this a
reminiscence of dancing to the guitar for Pring’s sailor, perhaps?
“Our canoe landed in order to give them some bagatelles, at which
they were greatly pleased. Some of them came to us and begged us
to go to their river. We weighed anchor to do so, but were unable to
enter on account of the small amount of water, it being low tide, and
were accordingly obliged to anchor at the mouth. I went ashore
where I saw many others who received us very cordially. I made also
an examination of the river, but saw only an arm of water extending a
short distance inland, where the land is only in part cleared up.
Running into this is merely a brook not deep enough for boats except
at full tide. The circuit of the Bay is about a league. On one side of
the entrance to this Bay there is a point which is almost an island,
covered with wood, principally pines, and adjoins sand banks which
are very extensive. On the other side the land is high. There are two
islets in this bay, which are not seen until one has entered and
around which it is almost dry at low tide. This place is very
conspicuous from the sea, for the coast is very low excepting the
cape at the entrance to the bay. We named it Port du Cap St. Louis,
distant two leagues from the above cape and ten from the Island
Cape [Gloucester]. It is in about the same latitude as Cap St. Louis.”
 (Larger)
New England

CAPTAIN JOHN SMITH’S MAP OF NEW ENGLAND, 1614

Reproduced from the Pequot Collection, Yale University Library

Champlain’s map of Plymouth Harbor, which is reproduced

herewith, was a quick sketch which he drew from the end of Long
Beach after his vessel went aground there, probably during the
afternoon of their arrival. Since the expedition stayed in Plymouth
Harbor only over one night, too much accuracy of detail must not be
expected of it. Saquish Head is represented as an island, and no
distinction is made between Eel River and Town Brook. Plymouth
Harbor has probably shoaled a good deal since the early
seventeenth century, since it would now be impossible to find a
seven-fathom anchorage anywhere except immediately around
Duxbury Pier Light; yet Champlain’s anchorage in the middle of
Plymouth Bay is so designated. Martin Pring had even described a
landlocked anchorage in seven fathoms. The chief value of
Champlain’s little map, aside from confirming the locality, is its
evidences of very extensive Indian houses and cornfields occupying
much of the slopes above the shore all the way around from the Eel
River area through Plymouth and Kingston to the shores of Duxbury
Bay.
The expedition left Plymouth on July 19 and sailed around the
shores of Cape Cod Bay before rounding the Cape and arriving the
next day at Nauset Harbor in Eastham. During several days’ stay
there, a French sailor was killed by the Indians in a scuffle over a
kettle. The following year, when Champlain returned to Cape Cod, a
more serious disaster occurred. Four hundred Indians at Chatham
ambushed and massacred five Frenchmen in a dawn raid, then
returned and disinterred their bodies after burial. The French took
vengeance by coolly slaughtering half a dozen Indians a few days
later. But, like the English adventurers, the French then abandoned
Massachusetts and never returned. Champlain reported that in all
his travels he had found no place better for settlement than Nova
Scotia. Two years later, changes of plans in France transferred him
to Quebec, where he spent the remainder of his career laying the
foundations of French Canada along the St. Lawrence.
Massachusetts Indians had again rebuffed the threat of European
penetration.
We have already noted that while Champlain was in
Massachusetts, George Waymouth and Martin Pring had been
exploring Maine. The coördination of these exploratory voyages was
largely the work of Sir Ferdinando Gorges, a diligent organizer of
New England colonial preparations. In 1606 the administrative
architecture of the English colonial movement in America was built.
King James gave charters to two companies, the London Company
and the Plymouth Company, providing for settlements respectively in
what came to be known as “Southern” and “Northern” Virginia. The
successful colony at Jamestown was founded by the London
Company in 1607. The coincident attempt by the Plymouth
Company, organized by Gorges, and the Popham and Gilbert
families, to found a colony on the Kennebec River in Maine failed
after a year’s trial. This Sagadahoc Colony failure was a blow to New
England colonization, the effects of which lasted for a generation,
since the impression of New England as a subarctic area, impractical
for settlement, remained in English minds for many years. It needs to
be emphasized, however, that despite this setback to English hopes,
the loss of fortunes invested in the enterprise, and the breakdown of
the Plymouth Company produced by this failure, the enterprise had
come much nearer to success than Humphrey Gilbert’s attempted
colony in Newfoundland. Much was learned about techniques of
living in the new country, getting along with Indians, and the need for
continuous replacement and supply. These ventures were
hazardous: they required courage, teamwork, strong leadership, and
personnel of heroic wisdom and tenacity.
After the Sagadahoc failure, the pattern of English activity on the
New England coast reverted for five years to the former state of
occasional trading and fishing voyages. The only events that
touched even remotely on Plymouth history were Cape Cod visits of
three men from different areas of activity. In 1609 Henry Hudson
landed briefly on Cape Cod on his way from Maine to his
explorations of the Hudson River which led to the Dutch claims in
that region. Samuel Argall from Virginia in 1610 likewise saw Cape
Cod on a voyage designed to supplement Jamestown’s failing food
supplies with New England codfish. And in 1611 Captain Edward
Harlow, sent on an exploring voyage to the Cape Cod region by the
Earl of Southampton, seems to have had five skirmishes with Indians
on Cape Cod and the Vineyard. Harlow’s vessel was attacked by
canoes while at anchor, and lost a long boat being towed astern to
the Indians, who thereupon beached her, filled her with sand and
successfully prevented the English from retaking her. Harlow
returned to England with little except five captured natives. Among
them was Epenow, an Indian whose treachery later accounted for
the death of Captain Thomas Dermer.
In 1613 the French fur-trading activities on the Bay of Fundy
were supplemented by an ambitious project to establish a Jesuit
missionary colony in that region. But this second French attempt to
colonize Maine was nipped in the bud after only a few weeks by Sir
Samuel Argall’s armed cruiser, sent from Virginia for the purpose.
This ended the threat of France as a colonial power in New England
except for occasional incursions into eastern Maine.
The year 1614 opened with a visitor to Plymouth from a new
quarter. Dutch fur traders, following in the wake of Henry Hudson’s
1609 discoveries, were already at work in the Hudson River. Two of
them, Adrian Block and Hendrick Christiansen, were about to weigh
anchor from Manhattan and depart for the Netherlands with a cargo
of furs in the fall of 1613 when one of their ships caught fire and
burned to the water’s edge. Both crews therefore stayed over the
winter on Manhattan Island, and there built a new “yacht,” the
Onrust, which they felt must be given a shakedown cruise before
attempting the Atlantic crossing. Block therefore sailed her eastward,
the first passage of Long Island Sound by a European, and explored
the Connecticut shore and rivers, Narragansett Bay and the Cape
Cod region, to all of which he laid claim for the Dutch as “Nieu
Nederlant.” Contemporary Dutch accounts offer us little of interest
about the Massachusetts phases of this voyage except some sailing
directions in Massachusetts Bay that suggest that Adrian Block
sailed from a place called Pye Bay, usually identified with Salem, to
the Lizard on the English Channel. But the Figurative Map which he
published in 1616 as a part of his report to the States General of the
Netherlands contains many additional details to which Dutch names
are applied, including a wholly unmistakable outline of Plymouth
Harbor, here called Cranes Bay. From this it seems obvious that
Block did visit Plymouth in the spring of 1614, and may be
considered as yet another of its explorers. It would be interesting to
know whether any of the Leyden Pilgrims, living in the Netherlands
for four years after the map’s publication, ever saw it before setting
out for the New World. In view of the controversy over whether the
Pilgrims were indeed headed for the Hudson River, it is interesting to
note that this map of Adrian Block’s would have been the most
accurate one available to them as a guide to the New York region,
yet there is nothing in the Pilgrim chronicles to suggest that they had
it with them on the Mayflower.
Also in 1614 there came sailing into Plymouth Harbor a man
whose map and writings were used by the Pilgrims, though he said
that they refused his advice and his leadership. Captain John Smith
would like to have been the founder of New England, but had to be
content to be its Hakluyt. He named New England, and “Plimouth,”
and Massachusetts, and the Charles River and Cape Ann—at least
he was the first to publish these names. He produced the best
known map of New England of that early period. He spent the last
seventeen years of his life writing the history of New England
voyages and pamphleteering for its settlement. Yet a succession of
misfortunes prevented him from ever revisiting the coast for which he
developed such enthusiasm during his three months’ voyage in
1614. Smith had already been governor of Virginia and had
experience in what it took to plant a successful colony. His writings
had unquestionably a strong influence on the Massachusetts colonial
undertakings, particularly since he was not afraid of Indians and
since he recognized the difference between the bleak coast of Maine
and the relatively better-situated Massachusetts area as a site for
colonial development.
John Smith arrived at Monhegan Island in Maine in April, 1614,
with two vessels. In the smaller of these he spent his time exploring
and mapping the coast from the Penobscot to Cape Cod, much as
Champlain had done nine years earlier. Thomas Hunt in the larger
vessel remained at Monhegan, fishing. Reaching “the Countrie of the
Massachusetts, which is the Paradise of all those parts,” Smith
entered Boston Harbor. “For heere are many Iles all planted with
corne: groves, mulberries, salvage gardens, and good harbours: the
coast is for the most part high clayie, sandie cliffs. The Sea Coast as
you passe, shews you all along large corne fields and great troupes
of well proportioned people; but the French, having remained heere
neere six weeks left nothing for us.” At Cohasset he wrote: “We
found the people in those parts verie kinde, but in their furie no lesse
valiant. For upon a quarrell we had with one of them, hee onely with
three others, crossed the harbor of Quonahassit to certaine rocks
whereby wee must passe; and there let flie their arrowes for our
shot, till we were out of danger,—yet one of them was slaine, and
another shot through his thigh.” His description of Plymouth, which
was variously known as Patuxet or Accomack, immediately follows
the Cohasset episode quoted above: “Then come you to Accomack,
an excellent good harbor, good land, and no want of anything except
industrious people. After much kindnesse, upon a small occasion,
wee fought also with fortie or fiftie of those; though some were hurt,
and some were slaine; yet within an hour after they became friends.”
In another passage he adds, “we tooke six or seven of their
Canowes which towards the evening they ransomed for Bever
skinnes.” Apparently Smith supplied a motive for the resumption of
friendship, knowing that the Indians could be bought off. This was
the kind of Indian policy Myles Standish used at times; in fact there is
a certain resemblance between the two men. In any case Smith left
for England with a cargo of beaver, and the Indians of Plymouth got
back their canoes.
But the next visitor to Plymouth, still in 1614, did not leave as
good an impression. With Smith departed for England, Thomas Hunt
appeared in Plymouth Harbor in Smith’s larger vessel. Not content
with a hold full of Monhegan codfish, Hunt now kidnaped twenty or
more Plymouth natives, stowed them below decks, and sailed away
to Spain, where he sold them into slavery at Malaga, “for £20 to a
man.” This was a typical seaman’s private venture, or side bet to the
profits of the codfish cargo. John Smith wrote that “this wilde act kept
him [Hunt] ever after from any more emploiment in those parts.”
Samuel Purchas termed Hunt’s “Savage hunting of Savages a new
and Devillish Project.” One can imagine what bitterness grew toward
the English among Massachusetts Indians after this demonstration
of European barbarism.
The quirks of history are at times worthy of the most fantastic
fiction. Thomas Hunt’s universally condemned crime happened to
produce one result which proved of great advantage to the Pilgrims.
Among the twenty wretched Plymouth natives whom Hunt sold at the
“Straights of Gibralter” was an Indian named Squanto. Then began a
five-year European education which trained Squanto for his
irreplaceable services to the Pilgrims as their interpreter. Squanto
was rescued by good Spanish friars, “that so they might nurture [him]
in the Popish religion.” In some unknown manner he reached
England and continued his education for several years in the
household of one John Slany, an officer of the Newfoundland
Company. His subsequent travels will appear in our discussion of
Thomas Dermer’s voyage in 1619. It is sufficient at this point to note
that perhaps the greatest blessing ever bestowed upon the Pilgrim
Fathers was the gift of a treacherous English shipmaster, a Spanish
Catholic friar, and an English merchant adventurer.
Things were going badly in another area of Massachusetts
during that eventful year of 1614. As though the expeditions of Block,
Smith, and Hunt were not sufficient for one year, Nicholas Hobson
now made his appearance at Martha’s Vineyard. Sent out by Sir
Ferdinando Gorges in an attempt to establish a fur-trading post in
that region, Hobson was using the Indian, Epenow, captured by
Harlow’s expedition in 1611, as his pilot through the shoals of
Nantucket Sound. Epenow cleverly contrived his escape, and a full-
scale battle ensued. “Divers of the Indians were then slain by the
English, and the Master of the English vessel and several of the
Company wounded by the Indians.” Hobson’s party “returned to
England, bringing nothing back with them, but the News of their bad
Success, and that there was a War broke out between the English
and the Indians.” Increase Mather later remarked that “Hunt’s
forementioned Scandal, had caused the Indians to contract such a
mortal Hatred against all Men of the English Nation, that it was no
small Difficulty to settle anywhere within their Territoryes.”
It was at this point in history that another strange series of
events took place, of much more far-reaching significance. With
English expeditions defeated and sent back to England empty-
handed, with an Indian war “broke out,” fate, or Providence, or
whatever you call that destiny which seems at times to intercede for
civilization in its remorseless quest for progress, now took a hand.
Some European disease, to which the natives had no resistance and
the Europeans complete immunity, swept the coasts of
Massachusetts clear of Indians. Suddenly it appeared in all the river
villages along the Mystic, the Charles, the Neponset, the North River,
and at Plymouth. No one knows what it was—whether chicken pox
or measles or scarlet fever. The Indians believed it was the product
of a curse leveled at them by one of the last survivors of a French
crew wrecked on Boston Harbor’s Peddock’s Island in 1615. By
analogy with what later happened to other primitive races in the
Americas and the Pacific islands, it was probably one of the
children’s diseases. The Indians died in thousands. A population of a
hundred thousand shrank to five thousand in the area from
Gloucester to New Bedford. “They died on heapes,” Thomas Morton
wrote, “and the living that were able to shift for themselves would
runne away and let them dy and let there Carkases ly above the
ground without buriall.... And the bones and skulls upon the severall
places of their habitations made such a spectacle after my comming
into those parts that as I travailed in that Forrest, nere the
Massachusetts, it seemed to mee a new-found Golgotha.”
Overnight the Indian war had vanished. Overnight the coast from
Saco Bay in Maine to Narragansett Bay in Rhode Island lay wide
open to European settlements. The cleared fields along the rivers
and salt marshes grew up to weeds, ready for the spade of the
English planter. For twenty miles inland the land was cleared of the
Indian menace in precisely the area where they had been most
agricultural, in what John Smith had called the “Paradise of all those
parts.” The choicest sites for plantations, at the river mouths and
along the tidal reaches of Boston Bay, Salem, Gloucester, and
Plymouth, were stripped of opposition. Beaver, deer, and codfish
multiplied unhindered. Smith’s description of Plymouth, “good harbor,
good land and no want of anything but industrious people,” was now
doubly true of the whole mainland shore of Massachusetts Bay.
These conditions were confirmed by Captain Thomas Dermer in
1619. Dermer had been associated with John Smith and Ferdinando
Gorges in an attempted New England voyage in 1615, and was
probably familiar with the coast. He was in Newfoundland in 1618
and there became acquainted with Squanto, who had been living in
the household of John Slany in England. Squanto’s European stay
was now completed, and someone had brought him out to
Newfoundland. Dermer appreciated how valuable he might prove to
be in a trading voyage to Massachusetts, and secured permission
from Governor John Mason of Newfoundland, and also from Sir
Ferdinando Gorges, to use him as a pilot for a Massachusetts
voyage.
Arrived in Massachusetts Bay, Dermer wrote: “I passed alongst
the coast where I found some ancient Plantations, not long since
populous now utterly void, in other places a remnant remaines but
not free of sickenesse. Their disease the Plague for wee might
perceive the sores of some that had escaped, who describe the
spots of such as usually die.” Reaching Plymouth, which, we
remember, was Squanto’s home, he goes on: “When I arrived at my
Savages native Country (finding all dead) I travelled alongst a daies
journey Westward, to a place called Nummastaquyt [Nemasket or
Middleboro], where finding Inhabitants I dispatched a messenger a
dayes journey further west to Poconokit, which bordereth on the sea;
whence came to see me two Kings; attended with a guard of fiftie
armed men, who being well satisfied with that my Savage and I
discoursed unto them—gave me content in whatsoever I
demanded.” At Poconokit he “redeemed a Frenchman, and
afterwards another at Mastachusit,” victims of shipwreck three years
before. What a chronicle these two castaways might have added to
Massachusetts history had their memoirs been preserved!
Squanto now found himself the only survivor of those two
hundred or more natives of Plymouth whom Martin Pring and
Champlain and John Smith had encountered. We note that he
brought the Englishmen of Dermer’s party into friendly association
with the sachems of Poconokit, which was Massasoit’s village at the
mouth of the Taunton River. This was the first friendly contact with
Massachusetts Indians in five years, the first since the criminal
barbarity of Thomas Hunt had aroused the enmity of the natives in
1614. We can read between the lines what a reconciliation the
homecoming of Squanto, himself a victim of that barbarous
kidnaping, must have produced among the Wampanoags. For
Dermer freed Squanto later, in 1619, and he found his way back to
Massasoit before the arrival of the Pilgrims. Whether Sir Ferdinando
Gorges or Dermer himself was responsible for this peacemaking
gesture, we have no way of knowing, but it seems to have cemented
again a long-standing peace between the English and the
Wampanoags, which was worth a whole battalion of soldiers to the
safety of New Plymouth. Captain Thomas Dermer, who probably
never heard of the Pilgrims, thus brought them peace. The Indian
war was ended.
It is therefore the more tragic that Dermer died of Indian arrow
wounds the next year after a battle with Epenow of Martha’s
Vineyard, an Indian captive who had not made peace with the
English. Had Epenow, instead of Squanto, lived at Plymouth, history
might have run quite differently. Captain Thomas Dermer may be
considered the first of the Plymouth martyrs, who lost his life after
saving a New Plymouth that did not yet exist, though the Mayflower
was on its way when he died.
It is a strange commentary on the justice of history that the men
who had spent their lives on New England colonization had almost
no share in the first successful plantation in Massachusetts. We
have seen what an outpouring of futile struggle men like Gorges and
Smith and Dermer had expended on the failures that set the stage
for the Pilgrims. It was now to fall to the lot of a group of English
exiles, who had lived twelve years in the Netherlands, to arrive by
accident in Massachusetts at the precise moment when the
merchant adventurers, whom they despised, had succeeded in
producing the conditions for success. The Pilgrim legend is well
founded, in the tribute it pays to the forthright courage and
persistence of the forefathers, but it ignores their utter dependence
on the maritime renaissance of England as the foundation on which
their success rested. The line of succession stemming from the
exploits of Drake and Hawkins and the ships that sank the Armada
carried directly on into the efforts of Gosnold, Pring, Gorges, Smith,
Hobson, and Dermer to set the stage for Plymouth. The fur trade and
the fisheries by which New Plymouth finally paid off its creditors had
been painstakingly developed by many hazardous years of
experiment by small shipowners of Bristol and Plymouth and other
smaller havens in the west of England. Faith in New England
ventures, so nearly destroyed by the Sagadahoc failure, had been
kept alive and sedulously cultivated by a little group of earnest men
around Gorges and John Smith, so that money could be available to
finance even the risky trading voyages necessary to keep a foothold
on the coast. We have seen how recently peace had been made
with the Indians.
The Pilgrims ascribed all these blessings to acts of Providence in
their behalf. But Providence has a way of fulfilling its aims through
the acts of determined men. Any visitor to Plymouth who reveres the
Pilgrims should also honor those representatives of the glorious
maritime energies of the Old World whose discoveries and
explorations prepared the way for permanent settlement. To them
also applies the phrase which Bradford used of the Plymouth
colonists:
“They were set as stepping-stones for others who came after.”
 Transcriber’s Notes
Punctuation, hyphenation, and spelling were made
consistent when a predominant preference was found in the
original book; otherwise they were not changed.
Simple typographical errors were corrected; unbalanced
quotation marks were remedied when the change was
obvious, and otherwise left unbalanced.
Illustrations in this eBook have been positioned between
paragraphs and outside quotations.
 *** END OF THE PROJECT GUTENBERG EBOOK EARLY
EXPLORERS OF PLYMOUTH HARBOR, 1525-1619 ***

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