Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting

Yu Kawamata
12/10/2016
1

Also see: Electrochemistry in Synthesis (Ambhaikar, 2005)

Electroorganic Chemistry (Rosen, 2014)

Unique parameters in electrochemistry:

Electrochemical cell ••••• devided or undivided
Current and potential ••••• constant current (c.c.) or constant potential (c.p.)
Electrolyte ••••• various ammonium or alkali metal salts
Electrodes ••••• anode (oxidation), cathode (reduction) Divided cell Undivided cell
• Anode compartment is always • Net reduction proceeds if a sacrificial
Topics not discussed: oxidation. anode is employed.
• Chemically modified electrodes • Cathode compartment is always • In other cases, reaction type (net oxidation
• Electrodes for inorganic and analytical electrochemistry reduction. or reduction) depends on the balance of
redox potentials of compounds in the cell.

1. Electrode material Review: Pletcher, Chem. Rev. 1990, 90, 837. 1-3. Overpotential
Overpotential is the potential
1-1. General Consideration
difference between a half-
i) Physical stability v) cost and lifetime reaction's thermodynamically
vi) suitable physical form determined potential and the
ii) chemical stability
potential at which the redox event
iii) overpotential vii) electrical conductivity is experimentally observed.
iv) rate and product selecticity
Thermodinamically defined potential:
1-2. Modes of action of electrodes Oxygen
O2 + 4H+ + 4e- 2H2O E ºred = 1.23 (V)
Electrodes can: transfer electrons
(vs SHE)
absorb organic compounds Hydrogen
Reactivity and product selectivity might be 2H+ + 2e- H 2 E ºred = 0.00 (V)
https://en.wikipedia.org/wiki/overpotential
affected by electrode materials.
act as reagents Generally, material with large O2 overpotential is used for anode and material
with large H 2 ovarpotential is used for cathode.
e.g. • Sacrificial anode (source of electron for
cathodic reduction)
1-4. Anode material
• NiOOH, PbO 2 anode
Sacrificial anode ••••• Al, Zn, Mg, steel etc.
• Ni and Pt cathode for hydrogenation anode
Non-sacrificial ••••• Pt, carbon based material
(graphite, glassy carbon,
RVC, BDD)
 Yu Kawamata Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting 2
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Sacrificial anode Source of electron for cathodic reduction Boron-Doped Diamond (BDD) Panizza, Electrochimica Acta, 2005, 51, 191.
Macpherson, Phys. Chem. Chem. Phys. 2015, 17 , 2935.
Top. Curr. Chem. 2012, 320, 1.
Mg Al Zn Fe Ni Sn Pb Cu Hg Ag Au Pt
• Highly durable under oxidative conditions
Dissolve when used as anode material
• Large O2 overpotential (1.1 V) and H 2 overpotential (-1.1 V)
Platinum • Due to its large O2 overpotential, OH radical and ozone can be generated
under aqueous conditions.
• Highly durable under oxidative conditions
• Used for waste-water treatment (complete mineralization of organic
• Wide potential range due to the large O2 overpotential molecule using OH radical) and ozone generation.
• Most common anode material • Recently introduced to electroorganic synthesis

Graphite
• Highly stable, but can be eroded under highly
oxidative conditions.
• Wide potential range due to the large O2 overpotential
• Absorption or intercalation of organic material
may occur.
• Most common anode material
BDD disk SEM image of BDD
Glassy carbon (Vitreous carbon)
Other anode material
• Amorphous form of carbon
• Very hard (as hard as quartz) Lead dioxide (PbO2) Review: Hampson, Chem. Rev. 1972, 72, 680.
• Good chemical stability and wide potential range • Large O2 overpotential, wide potential range.
• Prepared by electrochemical deposition of PbO 2 onto conductive materials
• Used for production of inorganic oxidant such as perchlorate, periodate
and ozone
• Electroorganic application is oxidation of alkenes, arenes and alcohols
Proposed structure of glassy carbon.
Glassy carbon rods All carbon atoms are sp2 carbon. Ni(O)OH anode Review: Petrosyan, Russ. J. Electrochem. 2010, 46, 1199.

Reticulated Vitreous Carbon (RVC) • Prepared by forming Ni(OH) 2 on Ni plate

Review: Ponce-de-León, J. Electroanal. Chem. 2004. 561. 203.
• Anodically stable only under basic conditions
.
• Oxidation of alcohol and amine proceeds by anodically generated Ni(III)
• Glassy carbon produced as a form on the electrode.
• Same chemical property as glassy carbon
Carbon sulfide electrode Review: Guillanton, Sulfur Reports. 1992, 12 , 405.
• Large surface area
• Sacrificial anode
.
SEM image of RVC • Used for thiolation of organic compounds
 Yu Kawamata Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting
12/10/2016 3
1-5. Cathode material 3. Electrode Degradation
High H 2 overpotential ••••• Carbon-based material, Pb, Sn, Hg, Cd, Zn Platinum anode Littauer, Corrosion Science, 1970, 10 , 29.

Useful for cathodic reduction of various Pt is known to be corroded slowly in the presence of halide ion.
organic molecules (corrosion rate: 5mgA-1h -1 in the electrolysis of 8 M HCl for 80 h)

Low H 2 overpotential ••••• Pt, Ni, Cu, Ag, Fe(steinless steel)

Graphite anode Hudson, J. Mater. Chem. 1997, 7, 301.
These electrodes are used when H 2 evolution Srivastava, J. Nanosci. Nanotechnol. 2015, 15 , 1984.
at cathode is desireble.
Generally, graphite is not tolerated under strongly oxidizing conditions or high
voltage due to the formation of graphene oxide.

Glassy carbon anode Isse, Mussini, Electrochem. Comm. 2010, 12 , 1531.

OH radical can cause erosion of glassy carbon
Conditions: H 2O2, Fe(NH 4)2(SO 4)2 and EDTA in 0.01 M acetate buffer
Example of reaction set-up with platinum
anode and mercury pool cathode
Wright, Chem. Soc. Rev. 2006, 35, 605

2. Price of Electrodes
Micrographs of GC surface: before treatment (left), after 60 min (right)
Material Supplier Quantity Price
BDD anode Comninellis, J. Appl. Electrochem. 2004, 34, 935.
Aldrich 1.5 g $ 480
Pt foil BDD is also known to be eroded under harsh electrchemical conditions.
Alfa Aesar 0.025 mm × 25 mm × 25 mm $ 107
Pt coated Ti ebay 30 mm × 40 mm $ 12.8

Graphite many 1 lb < $ 10

Glassy carbon rod Alfa Aesar 3 mm × 25 mm × 25 mm $ 98

RVC KRRaynolds 40 mm × 40 mm $15

BDD windsor scientific 3 mm diameter $ 305

Hg Aldrich 1 kg $ 422
Al, Mg, Ni, Cu, many Before electrolysis After severe anodic polarization at
1 lb < $ 10
Pb, Sn, Fe, Zn
1Acm -2 in 1 M HClO 4 for 576 h at 40 °C
 Yu Kawamata Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting
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4. Selected Electroorganic Reactions and Suitable Electrodes

Oxidation of amides and carbamates (Shono oxidation)
4-1. Anodic oxidation
O O
Oxidation of carboxylic acids (Kolbe reaction) Review: Schäfer, Chemistry and O
Physics of Lipids, 1979, 24, 321. anodic oxidation R MeOH R
R N N
anodic oxidation N
RCOO R R R OMe
-CO2
Anode: Pt (most common), Glassy carbon
Cathode (not critical): Pt, carbon, Fe, Hg etc. Anode: Pt, graphite
Cathode (not critical): Graphite, stainless steel, Pt,
Hetero coupling Boland, Steckhan, Tetrahedron Lett. 1996, 37, 8715.
Pt anode O
O steel cathode Application to toal synthesis Braekman, Daloze, Eur. J. Org. Chem. 2000, 2057.
MeONa
+ HOOC COOEt CO2Me CO2Me O
5 MeOH, c.c. graphite anode
COOH COOEt O
4.2 eq undivided cell 5 R N graphite cathode R N OMe
43% R N
Steel cathode was chosen to avoid catalytic hydrogenetion of the double bond. Et 4NOTs, MeOH
R = nC5H11 c.c., undivided cell
Cascade cyclization Schäfer, Synthesis, 1995, 1432.
78% (+)-calvine
O Me Regioselectivity of methoxylation is usually kinetic control, i.e., less substituted
O O α-position is functionalized preferentially.
Pt anode H Me
steel cathode
+ MeCO2H + Late-stage functionalization of polycyclyc lactams
5 eq MeOH, KOH, c.c.
undivided cell Aubé, Angew. Chem. 2015, 127 , 10701.
CO2H
42% 15% O graphite anode O OMe
graphite cathode
Effects of anode material Bretle, J. Chem. Soc. Perkin Trans. I, 1973, 257. N N
anode anode LiClO 4, MeOH
CO2Et c.c. undivided cell CO2Et
Pt cathode Pt 62%
COOH 91% (dr = 4:1)
4 4 Graphite 5-9%
4 Et 3N, EtOH, c.c.
10 other examples
undivided cell RVC 45-53%
Major products with graphite anode A mobile phone charger was used as a power supply.
O O O
O O O
4 4 4 4
Platinum anode gives radical intermediates, whereas graphite anode gives
cationic intermediates.
 Yu Kawamata Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting
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Oxidation of peptides Papadopoulos, Steckhan, Tetrahedron, 1991, 47, 563. Oxidation of electron-rich π-system
Pt anode Me O Anode: Pt, graphite, RVC, BDD
O Me O Cathode: Pt, graphite
H Pt cathode
N
Ph N OMe Bz N NH
H Et 4NCl, MeCN/MeOH Application to a natural product synthesis Moeller, J. Am. Chem. Soc. 2004, 126 , 9106.
O Me Me CO2Me
c.c, undivided cell
84% (1.5:1 dr) RVC anode O
TBSO Me
anodically graphite cathode
generated Cl+ 2,6-lutidine, LiClO 4

O Me Cl O O Me O TBSO MeOH/CH 2Cl2 TBSO

O O
N N c.c. undivided cell
Ph N OMe Ph N OMe
H H MeO
O Me O Me most electron-rich O
O
Unusual oxidation Shono, J. Am. Chem. Soc. 1990, 112, 2369. TsOH
O OH
Pt anode HO
Pt cathode OMe O
halide additive O
NHTs + 88%
OMe (+)-Alliacol A
MeONa, MeOH N
NHTs Ts C-H arylation Yoshida, Angew. Chem. Int. Ed. 2012, 51, 7259.
c.c., undivided cell
1 2 OMe
carbon felt anode
additive: KBr 30% 22% OMe Pt cathode naphthalene
KI 82% - Bu 4NB(C 6F 5)4 (1 eq.)
radical
cation Br OMe
Proposed mechanism: CH2Cl2, -90 ºC,
Br OMe
OMe OMe c.c., divided cell
6 eq.
R Br R X+ R R
N NHTs NHTs 73%
MeOH NTs
Ts Br 9 other examples
MeOH
N-Br bond
C-H amination Yoshida, J. Am. Chem. Soc. 2013, 135 , 5000.
homolysis
1
carbon felt anode
R Hofmann-Loffler-Freytag Pt cathode
N 2 NH 2
pyridine N piperidine
Ts
Bu 4NBF 4, MeCN MeCN, 80 ºC
c.c., divided cell
99%
12 other examples
 Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting
Yu Kawamata
12/10/2016
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Organocatalyzed oxidation Boydston, J. Am. Chem. Soc. 2012, 134 , 12734.
Oxidation of other compounds
graphite anode BF 4
O Pt cathode Though choice of electrodes varies, Pt is often the first choice for anode.
O
+ R' OH S N Ar
R H 10 mol% cat., DBU, TBAB R OR'
c.p., undivided cell
> 20 examples Me Electrochemical aziridination Yudin, J. Am. Chem. Soc. 2002, 124 , 530.
Proposed mechanism catalyst
O Pt anode
Pt cathode
N NH 2 + Phth N
Graphite cathode gave inferior HNEt 3OAc, MeCN
effect due to the sluggish H 2 O c.p., divided cell 85%
evolution. 13 other examples
This reaction didn't work with graphite anode due to competing alkene
oxidation on graphite.

Effects of anode material Coupling of phenols on BDD Waldvogel, Euro. J. Org. Chem. 2006, 4569.

Nyberg, Acta Chem. Scand. B. 1978, 32, 157. BDD anode

OH Me OH Me
OAc Ni cathode
Me anode Me Me [Et 3NMe]O 3SOMe
Pt cathode OAc
+ H 2O, 70 ºC
AcOH, AcONa
Me Me c.c., undivided cell Me Me c.c., undivided cell Me HO Me
Me Me Me
3 4 49%
Me Me
anode: Pt 3/4 = 4.4 (19% yield) O
Glassy carbon 3/4 = 21 (35% yield) O
was obtained with Pt anode.
Nishiyama, Angew. Chem. Int. Ed. 2012, 51, 5443. H
Me Me
OMe OTBDPS OMe
anode MeO OMe Oxidation of phosphorus Ohmori, J. Chem. Soc. Chem. Commun. 1995, 871.
Pt cathode CHO
OTBDPS
+ graphite anode
KOH, MeOH graphite cathode
OMe c.c., undivided cell O 3 eq. nBu 3P OH O
MeO OMe OMe
2 eq. MeSO 3H
anode: Pt 100% 0%
COOH
BDD 100% 0% BnNEt 3Cl, CH2Cl2
5 6
glassy carbon 0% 100% undivided cell, c.c.
63% (trans:cis=81:19)
Generation of MeO was confirmed in the case of Pt and BDD as anode. 6 other examples
 Yu Kawamata Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting 7
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Mechanism:
Shono, J. Am. Chem. Soc, 1986, 108 , 4676, Shono, J. Org. Chem. 1994, 59, 1407.
nBu 3P
graphite anode Me OH
O O Sn cathode H
5 nBu 3P
OPnBu 3 PnBu 3
nBu 3PCl 2 O Et 4NOTs, iPrOH
-nBu 3PO
O O c.c., divided cell
anode 70% single diastereomer
O >20 examples
OH O OH OH
PnBu 3 Cu, Ag, Pb, Zn and Pb cathode gave lower yields, whereas Pt, Ni and Ti
PnBu 3
- nBu 3P gave no desired product.
OH cathode
6
Reduction of esters Shono, J. Org. Chem. 1992, 57, 1061.

Mg anode
Oxidation of sulfur Matsumoto, Yoshida, Asian J. Org. Chem. 2013, 2, 325.
Mg cathode
carbon felt anode O LiClO 4
SAr R OH
Pt cathode Ph R OMe
Bu 4NB(C 6F 5)4 Me Ph tBuOH, THF 70-90%
ArSSAr
ArSSAr Me R=alkyl c.c., undivided cell
CH2Cl2, -78 ºC SAr SAr
Me
Ar=4-FC6H 4 c.c., divided cell tBuOH
78%
same conditions OH 60%
11 other examples as above
CO2Me
4-2. Cathodic reduction O OMe
TMSCl
OTMS 67%
Reduction of carbonyl group Grimshaw, Electrochemical reactions and
mechanism in organic chemistry, Elsevier, 2000. Esters are not reduced with Zn, Pb, Ni, Cu, Pt and C cathode
Anode: Pt, graphite, sacrificial anodes
Cathode: Hg, Sn, Mg, Pb, Pt, graphite
Reduction of amides Waldvogel, Euro. J. Org. Chem. 2014, 5144.

Reductive cyclization of ketones Shono, J. Am. Chem. Soc. 1971, 93, 5284. Pt anode
Shono, J. Am. Chem. Soc. 1978, 100 , 545. Pb cathode
O electrolyte, H 2SO 4
graphite anode HO
Me
graphite cathode Ph NH 2 Ph NH 2
Me MeOH, c.c
62%
Et 4NOTs, dioxane/MeOH divided cell
O c.p., divided cell
66% (single diastereomer) 10 other examples including 2º and 3º amine product
6-membered & piperidine ring formation and transannular cyclization were
also demonstrated.
 Yu Kawamata Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting
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Reduction of alkenes and conjugated alkenes Grimshaw, Electrochemical reactions An example of notable anode effect Nédélec, J. Org. Chem. 1990, 55, 2503.
and mechanism in organic chemistry,
Anode: Pt, graphite, sacrificial anodes Elsevier, 2000. Al anode MeO
Cathode: Hg, Sn, Mg, Pb, Zn, Pt, graphite MeO 2C CO2Me steel cathode CO2Me Br
O
+
Al
Reduction of dienes Shono, J. Org. Chem. 1992, 57, 5561. Br Br NBu 4BF 4, NBu 4I, CO2Me
NMP, c.c. O
undivided cell 50% MeO
Mg anode iPr
Mg cathode Mg
+ Mg, Zn anode • • • yield < 10%
OH
CO2Me
LiClO 4, THF
c.c., undivided cell Reduction of other compounds
62% intermediate Anode: Pt, graphite, sacrificial anodes
Pt, Al, Zn, Ni, Cu, Pb as cathode • • • 0% Cathode: Materials with large H 2 overpotential
same conditions OH
Me as above Reductive carbon-halogen bond cleavage Waldvogel, Chem. Euro. J. 2015, 21, 13878.
+ MeCO 2Me Me
Ph Me Br Pt anode H
Ph
Leaded bronze cathode
94% (single diastereomer) Br H
[Et 3NMe]O 3SOMe
Reduction of unsaturated esters
• Dimerization NIshiguchi, Angew. Chem. Int. Ed. 1983, 22, 52. N H 3PO 3, MeCN, c.c. N
Boc COOH divided cell Boc COOH
Pt anode CO2Me
Cu cathode Ph
Leaded bronze was found to be more tolerant against corrosion than pure lead.
2 Ph CO2Me O
TBAOTs, DMF
c.p. divided cell Ph Birch reduction Kariv-Millar, J. Org. Chem. 1983, 48, 4210.
76%
• Natural product synthesis Little,Tetrahedron Lett. 1990, 31, 485. Me OH steel anode Me OH
Hg cathode
H O CO2Me
OH Bu 4NOH, THF
O O H CO2Me
Hg cathode c.c. undivided cell
O MeO MeO
H TBABr, MeCN 92%
quadrone 89% (combined yield Electrochemical transition-metal catalysis Durandetti, J. Org. Chem. 1997, 62, 7914.
with minor diastereomer) Al anode
e- O O O O
NC Ni cathode
OTBDPS NC OTBDPS
MeN N
Me
+ PhI TBABF4, NiBr 2bpy MeN N * Me
5 steps
HO Cl Ph
DMF, c.c.
CHO H Ph Ph
undivided cell
(slow addition) 57%, 90% ee
 Yu Kawamata Electroorganic Chemistry: Choice of Electrodes Baran Group Meeting
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Mechanism: Useful material for electroorganic synthesis

NiBr 2(bpy)
Redox potential of organic coumpounds Nicewicz, Synlett, 2016, 27, 714.
cathodic reduction

Ni(0) II R-Cl
PhI Ni Ph R Ph
I cathodic
reduction

This step might be similar to Weix's system.

Weix, J. Org. Chem. 2014, 79, 4793.
Weix, J. Am. Chem. Soc. 2013, 135 , 16192.

Summary

Anode material

Do you use sacrificial anode?

yes no Reviews for further study

I don't know
• Indirect (mediated) electrolysis
(a) Steckhan, Angw. Chem. Int. Ed.1986, 28, 683.
Al, Zn, Mg, Fe etc. Pt, carbon based material
(b) Little, Chem. Soc. Rev. 2014, 43, 2492.

Cathode material • Application to complex molecule syntheses

(a) Wright, Chem. Soc. Rev. 2006, 35, 605.
Is your target reaction reduction? (b) Moeller, Tetrahedron, 2000, 56, 9527.

yes no • Electrochemical halogenation

Petrosyan, Russ. J. Electrochem. 2013, 49, 497.
I don't care
Hg, Pb, Sn, Mg, and Whatever • Electrochemistry with transition-metal catalysis
Is H 2 evolution OK? conductive
other material with large Duñach, Euro. J. Org. Chem. 2003, 1605.
H 2 overpotential
yes no

Pt, Ni, Fe and other carbon based material

material with small H 2 and other material with
overpotential large H 2 overpotential