SPS Photochemistry

Physical Organic Photochemistry and
Basic Photochemical Transformations
H
H
O
O
Me
Me
Group Meeting
Jan 26th 2011
h (310 nm)
Benzene
OHC
Scott Simonovich
H
O
H
Me
Me
Electromagnetic Radiation
UV
Vis
IR
W
Radio
(nm)
E (kcal/mol)
200
143
300
95
400
72
500
57
600
48
700
41
1,000
29
5,000
10,000
107
3 X 10-2
109
3 X 10-4
1011
3 X 10-6
(nm)
E (kcal/mol)
200
143
300
95
400
72
500
57
600
48
700
41
1,000
29
5,000
10,000
107
3 X 10-2
109
3X
10-4
1011
3 X 10-6
Group
UV
Vis
IR
W
Radio
(nm)
180
C
220
260
282
280
350
UV
Vis
IR
W
Radio
(nm)
E (kcal/mol)
200
143
300
95
83
400
72
35
500
57
99
600
48
111
700
41
73
1,000
29
86
5,000
146
10,000
180
107
3 X 10-2
109
3 X 10-4
X-rays and gamma-rays lead to ionization
1011
3 X 10-6
UV/Vis for electronic absorption
BDE (kcal/mol)
IR for nuclear vibrational motion (IR)

W for electron spin precession (EPR)
Radio for nuclear spin precession (NMR)
Jablonski Diagram
Sn
S2
Tn
S1
T2
T1
h
S0
Stark-Einstein law - molecule will absorb light to excite a single electron and
energy of light must match difference between S0 and S*
High probability transitions usually occur with conservation of spin
Jablonski Diagram
Sn
S2
Tn
S1
T2
T1
h
S0
Kasha's rule - relaxation to S1 is very rapid compared to other processes
Jablonski Diagram
Sn
S2
Tn
S1
T2
T1
h
S0
Radiative decay to ground state (fluorescence or phosphorescence)

Non-radiative decay (heat or energy transfer)
Intersystem crossing to different manifold
Jablonski Diagram
Sn
S2
Tn
S1
T2
T1
h
S0
Photochemistry occurs from S1 (infrequent) or T1 states

Photochemistry must compete with photophysical processes
Jablonski Diagram
Sn
S2
Tn
S1
T2
T1
h
S0
Photochemistry occurs from S1 (infrequent) or T1 states

Photochemistry must compete with photophysical processes
If excited state is short-lived, there will be less time for chemistry
Photoreaction must generally have Ea less than 20 kcal/mol
S1 reactions will not outcompete fluorescence if Ea is above 10 kcal/mol
Allowed and Forbidden Processes
S1
T1
T1
S0
S0
S1
spin allowed
spin forbidden
spin forbidden
(excitation)
(excitation)
(ISC)
Spin forbidden transitions alter electron spin angular momentum

Triplet states tend to be more photochemically active b/c they are long-lived
Allowed and Forbidden Processes
S1
T1
T1
T1
S1
S0
S0
S1
S0
S0
spin allowed
spin forbidden
spin forbidden
spin forbidden
spin allowed
(excitation)
(excitation)
(ISC)
(ISC, phosphorescence)
(IC, fluorescence)
Spin forbidden transitions alter electron spin angular momentum

Triplet states tend to be more photochemically active b/c they are long-lived
Bimolecular Photophysical Processes

How could one access T1 exclusively?
S1(n, *)
slow
T1(n, *)
S0

S1(n, *)
slow
T1(n, *)
S0
S1(n, *)
fast
T1(n, *)
S0
DONOR

S1(n, *)
slow
T1(n, *)
S0
S1(n, *)
S1(n, *)
fast
T1(n, *)
T1(n, *)
S0
S0
DONOR
ACCEPTOR
Sensitization
D* + A
D + A*
sensitizer
triplet energy
(kcal/mol)
acetophenone
73.6
benzophenone
68.5
anthraquinone
62.2
biacetyl
54.9
Sensitizer should absorb at a different wavelength than acceptor molecule

Triplet energy of senitizer must be greater than that of acceptor
Two mechanisms for photosensitization

Quenching requires close contact between A* and Q
Olefins and dienes are often used as quenchers
k1
A*
A*
A
kq
A
Stern-Volmer quenching kinetics
1/2 = 1/1 + kq[Q]

1 = lifetime of A* without Q
2 = lifetime of A* with Q
Description of quenching efficiency

k1
A*
A*
A
kq
A
1/2 = 1/1 + kq[Q]
Photoinduced electron transfer - leads to quenching of fluorescence
LUMO
LUMO
HOMO
HOMO

k1
A*
A*
A
kq
A
1/2 = 1/1 + kq[Q]
Photoinduced electron transfer - leads to quenching of fluorescence
LUMO
LUMO
HOMO
HOMO
Photochemistry
S*
photophysics
= quantum yield =
I
photochemistry
P1
P2
P3
P4
radical/ion chemistry
# molecules that undergo a process

# of photons absorbed by starting material
Photochemistry
S*
photophysics
= quantum yield =
I
photochemistry
P1
P2
P3
P4
radical/ion chemistry
# molecules that undergo a process

# of photons absorbed by starting material
Photophysical rates must provide an excited species that persists long enough for photochemistry to occur
Rate of photochemistry from S1 must outcompete fluorescence
Phosphorescence from T1 to S0 must be slow compared to photochemistry
Two or three energy surfaces are involved due to excited states
Three types of photochemical reaction diagrams
Photochemistry
Diabatic photoreaction
SM*
I
E
SM
Nuclear Movement
Small gap between surfaces promotes crossing

Minimum on upper surface matches maximum on ground state surface
Frequent return back to SM results in low quantum yield
Photochemistry
Diabatic photoreaction
SM*
I
S1 (SM)
E
S0 (SM)
S0 (pdt)
SM
Nuclear Movement
Small gap between surfaces promotes crossing

Minimum on upper surface matches maximum on ground state surface
Frequent return back to SM results in low quantum yield
Photochemistry
Adiabatic photoreaction
S1
E
S0
Nuclear Movement
Transition to excited state, which has smaller energy barrier

Initially generates product in excited state
Photochemistry
Adiabatic photoreaction
S1
S1 (SM)
S1 (pdt)
E
S0 (SM)
S0
S0 (pdt)
Nuclear Movement
Transition to excited state, which has smaller energy barrier

Initially generates product in excited state
Photochemistry
Hot Ground State reaction (thermal)
S1
E
S0
Nuclear Movement
Occurs when rate of internal conversion is much faster than photochemistry excited surface
Before energy is lost to collisions with solvent, chemistry in ground state occurs
Photochemistry
Hot Ground State reaction (thermal)
S1
S1 (SM)
S1 (pdt)
E
S0 (SM)
S0
S0 (pdt)
Nuclear Movement
Occurs when rate of internal conversion is much faster than photochemistry excited surface
Before energy is lost to collisions with solvent, chemistry in ground state occurs
Tendencies of S and T states

Singlet and triplet excited states often show different reactivity
Singlet
tend to have considerable zwitterionic character
undergo rapid, concerted reactions
stereospecific
must compete with facile photophysical processes
electrocyclic rearrangements
cycloadditions
sigmatropic rearrangements
Tendencies of S and T states

Singlet and triplet excited states often show different reactivity
Singlet
Triplet
tend to have considerable zwitterionic character
tend to have biradical character
undergo rapid, concerted reactions
triplet state is longer lived
stereospecific
stepwise reactions
no stereospecificity
must compete with facile photophysical processes

hydrogen abstraction
electrocyclic rearrangements
additions to unsaturation
cycloadditions
homolytic fragmentation
sigmatropic rearrangements
radical rearrangements
Different products due to the fact that the ground state is a singlet state
Olefin Isomerization
Simple olefins do not absorb at easily-generated wavelengths, so additional chromophores are added
h
313 nm
photostationary state
h
313 nm
Complete conversion to one isomer is difficult b/c both isomers absorb

Ratio controlled by absorption and quantum yield for isomerization
h
313 nm
Complete conversion to one isomer is difficult b/c both isomers absorb

Ratio controlled by absorption and quantum yield for isomerization
trans and cis stilbene absorb with the same efficiency at 313 nm
lifetime of S1(trans) = 68 ps
lifetime of S1(cis) = 1 ps
(trans to cis) = 0.50

(cis to trans) = 0.35
Olefin isomerization is a powerful feature of photochemistry
The relative energy of two minima on So surface does not matter
Key issue is how system exits from S1 or T1 onto S0
t-Bu
t-Bu
5%
95 %
isolated in matrix
t-Bu
t-Bu
5%
95 %
isolated in matrix
3-4 (impossible); 5 (difficult, reactive); 6-7 (facile, reactive); 8 or above (stable)

Cyclic trans olefins are used in situ for functionalization
Ph
h, ROH
Ph
isolated
Ph
h, ROH
Ph
Ph
Ph
OR
Ph
h, ROH
Ph
isolated
Ph
Ph
h, ROH
Ph
Ph
OR
Me
Me
Me
Me
h, H+
xylene
Me
Me
Me
Me
Me
Me
Me
Me
Photoadditions/substitutions
Hydrogen abstration is frequent in these reactions:

Strength of bond being broken
Strength of bond being formed
Steric effects of approach
Solvent effects on reagent or transition state
Photoadditions/substitutions
Hydrogen abstration is frequent in these reactions:

Strength of bond being broken
Strength of bond being formed
Steric effects of approach
Solvent effects on reagent or transition state
OH
OH
+
Ph
Ph
Ph
Ph
O
Ph
h
Ph
OH
Ph
Ph
OH
Ph
Ph
Ph
OH
Ph
OH
+
Ph
Ph
Ph
Ph
Norrish Type II
Intramolecular H abstraction
O
R
OH
R
O
R
OH
HO
+
R
Norrish Type II
Intramolecular H abstraction
OH
R
OH
HO
Six-membered H abstracted preferntially

Seven- and five-membered H abstraction possible if six-membered position is blocked or disfavored
O
Ph
OH
HO
Me
Ph
Me
60%
Norrish Type II
O
t-Bu
Me
t-Bu
+
Me
Me
Me
OH
t-Bu
Me
Me
Norrish Type II
O
t-Bu
Me
t-Bu
+
Me
Me
Me
OH
t-Bu
Me
Me
Stereospecificity of singlet and triplet states - Example: disproportionation in Type II reactions
OH
Et
Me
Et
Me
Et
fast
OH
h
3sens
Me
O
Et
R
Me
slow
Et
R
Me
Alkene Hydrogen Abstraction

Alkenes abstract hydrogens when excited to T1, but act as zwitterions if excited to S1 (and cannot isomerize)
Ph
Ph
Ph
Ph
i-PrOH
Me
Me

Ph
Ph
Ph
Ph
i-PrOH
Me
Me
h
3xylene
i-PrOH
Me
Me
Me Me
OH
Me
Me
Me
Me

Ph
Ph
Ph
Ph
i-PrOH
Me
Me
Me
Me
Me
Me Me
OH
3xylene
Me
i-PrOH
Me
Me
Ph
HO
h
HO
Ph
Ph
Ph
Me
Ph
Ph
Ph
O
Me
Ph

Ph
Ph
Ph
Ph
i-PrOH
Me
Me
Me
Me
Me
Me Me
OH
3xylene
Me
i-PrOH
Me
Me
Ph
HO
h
HO
Ph
Me
Ph
Ph
Ph
O
Me
Ph
Ph
Ph
HO
h
3xylene
Ph
Ph
HO
Me
Ph
Ph
HO
Ph
Me
+
Ph
Norrish Type I Fragmentation

C=O bond is a very strong bond, so there is a considerable driving force to reform it
O
R1
h
R2
(n, *)
R1
O
R2
R1
R2
Several factor control rate of this -cleavage reaction

C=O bond is a very strong bond, so there is a considerable driving force to reform it
O
R1
h
R2
(n, *)
R1
O
R2
R1
R2
Several factor control rate of this -cleavage reaction

Rate of Type II reaction, phosphorescence, or ISC
Nature of R1 and R2
Stability of resulting radical
Me = 103 s-1
1o alkyl = 107 s-1
Benzyl = 1010 s-1
Ring strain
h
O
O
Me
Me
O
Me
Me
Me
Me
Me
Me
h
O
O
Me
Me
O
Me
Me
Me
Me
Me
Me
H
Me
Me
h
O
O
Me
Me
O
Me
Me
Me
Me
Me
Me
Me
Me
h
O
O
O
CO2
Electrocyclic Reactions
Reversal of Pericyclic Selection Rules
Me
D C
2 h
Me
Me
dis.
Me
4 h
6 h
8 h
Me
Me
Me
h
con.
Me
Me
Me
D C
2 h
dis.
Me
Me
4 h
6 h
8 h
Me
Me
h
con.
Me
Me
Me R
Me R
Me
Me
con.
H
HO
HO
Me
Me
D C
2 h
dis.
Me
Me
4 h
6 h
8 h
Me
Me
h
con.
Me
Me
Me R
Me R
Me
Me
con.
H
HO
HO
O
O
O
O
O
dis.
H
Pb(OAc)4
H
Sigmatropic Rearrangements
Orbital Symmetry Rules control what rearrangements are allowed
Me
Me
H
h
h
Me
H
Me
H
Me
Me
H
Me
H+
nodes
3
2
LUMO
HOMO
Me
Me
H
Me
H+
Thermally disallowed
X
nodes
3
2
LUMO
HOMO
Me
Me
Me
H+
Thermally disallowed
X
nodes
nodes
LUMO
HOMO
2
1
0
LUMO
HOMO
1
0
Photochemically
allowed
h
Me
H
Me
H+
nodes
5
4
3
LUMO
HOMO
1
0
Me
H
h
Me
H
Me
H+
nodes
5
4
3
LUMO
HOMO
1
0
Me
H
h
Me
Me
H
Me
H+
nodes
nodes
LUMO
HOMO
LUMO
HOMO
0
rare for antarafacial shift to occur
Cycloadditions
Photochemical [2 + 2] cycloaddition
nodes
nodes
LUMO
HOMO
LUMO
HOMO
Cycloadditions
Photochemical [2 + 2] cycloaddition
nodes
nodes
LUMO
HOMO
LUMO
HOMO
nodes
nodes
1
HOMO
LUMO
HOMO
Cycloadditions
Acyclic olefins tend to undergo isomerization rather than [2 + 2]
= 0.04
= 0.5
h
R
= 0.04
Cycloadditions
Acyclic olefins tend to undergo isomerization rather than [2 + 2]
= 0.04
= 0.5
h
R
= 0.04
Small and medium ring cyclic olefins do, however, generally undergo facile [2 + 2]
Cycloadditions
DeMayo reaction - [2 + 2] with 1,3-diketone followed by retro-aldol
OH
Me
OH
retro-aldol
Me
O
O
base
O
Me
Cycloadditions
DeMayo reaction - [2 + 2] with 1,3-diketone followed by retro-aldol
OH
Me
OH
retro-aldol
Me
O
O
base
O
Me
S1 [4 + 2] is not allowed by orbital symmetry, but radical T1 undergoes stepwise addition
h
3sens
Cycloadditions
Paterno-Buchi reaction - stereospecificity
Me
O
H
Me
Me
Me
S1
95 %
Note that carbonyl/alkene [2 + 2]

occurs from both S1 and T1 states
Me
h
Me
O
Ph
T1
Me
90 %
Me
Cycloadditions
Paterno-Buchi reaction - stereospecificity
Me
Me
Me
Me
S1
95 %
Note that carbonyl/alkene [2 + 2]

occurs from both S1 and T1 states
Me
Me
Ph
Me
Me
T1
90 %
Paterno-Buchi reaction - regioselectivity with electron rich olefins
O
Ph
Ph
Me
Me
Me
O
Ph
Me
Ph Me
90 %
O
Ph
Ph
10 %
Me
Cycloadditions
Paterno-Buchi reaction - regioselectivity with electron rich olefins
O
Ph
Ph
Me
Ph
Me
Ph
90 %
= 0.5
10 %
Me
O
Ph
Me
Me
Me
Ph
Ph Me
Me
Ph
Me
Ph
Ph
Me
Oxygen radical is more electrophilic than carbon radical, so it adds first to form the more stable biradical
OR
Me
Me
Me
Me
OR
Me
OR
Me
Cycloadditions
Paterno-Buchi reaction - electron poor olefins
Only occurs from S1 state, so reactions are complete stereospecific
Products are not the expected adducts based on electron-rich alkene mechanism
Me
CN
O
Me
NC
CN
S1(n, *)
O
Me
Me
CN
Cycloadditions
Me
CN
O
Me
NC
CN
S1(n, *)
O
Me
CN
Me
Me
O
Me
Me
CN
Me
S1(n, *)
O
Me
Me
CN
Cycloadditions
Me
CN
O
Me
NC
CN
S1(n, *)
O
Me
CN
Me
Me
O
Me
Me
CN
Me
S1(n, *)
CN
Me
Me
O
Me
Me
NC
CN
T1(n, *)
CN
NC
Cycloadditions
Me
CN
O
Me
NC
CN
S1(n, *)
O
Me
CN
Me
Me
O
Me
Me
CN
Me
S1(n, *)
CN
Me
Me
O
Me
Me
O
Me
Me
NC
CN
T1(n, *)
CN
Me
T1(n, *)
CN
NC
NC
CN
Me Me
Cycloadditions
Me
CN
O
Me
NC
CN
S1(n, *)
O
Me
CN
Me
Me
O
Me
Me
CN
Me
S1(n, *)
CN
Me
Me
O
Me
Me
O
Me
Me
NC
CN
T1(n, *)
CN
Me
T1(n, *)
CN
NC
NC
CN
Me Me
Cycloadditions
Me
O
Me
Me
Me
O
Me
Me
CN
Me
S1(n, *)
CN
Me
Me
CN
O
Me
Me
Me
CN
Carbon radical is more nucleophilic than oxygen, so it adds first to make the more stable biradical
Cycloadditions
Cycloadditions of alkenes with enones are efficient reactions as well
h
Me
Me
Me
Me
90 %
O
+
-
Me + Me
Examples in Synthesis
H
N
sunlight
air, MeCN
NH
N
H
H
N
(con.)
H
N
NH
N H
H
NH
H N
N
H
91%
Ac
N
N
Ac
Ac
N
h, iPr2NEt, CH2Cl2
Br
(con.)
N
Ac
N
O
O
TsO
TsO
OTs
OTs
96%
Berlinck, R. G., et al. J. Org. Chem. 1998, 63, 9850.

Kobayashi, Y., Fujimoto, T., Fukuyama, T. J. Am. Chem. Soc. 1999, 121, 6501.
O
O
O
O
O
h, benzene
OH
OH
O
O
O
O
O
68%
Kraus, G. A., Chen, L. J. Am. Chem. Soc. 1990, 112, 3464.
O
O
O
O
O
h, benzene
OH
OH
O
68%
CHO
h (310 nm)
O
Me
O
Me
cyclohexane
O
Me
O
Me
H Me Me
92%
Kraus, G. A., Chen, L. J. Am. Chem. Soc. 1990, 112, 3464.
Lin, C. -H., Su, Y. -L., Tai, H. -M. Heterocycles, 2006, 68, 771.
Br
Me
Me
HO
1. Bu3SnH
AIBN
2. h, benzene
Me
Me
Me
Me
HO
HO
H
O
O
Me
Me
48%
Cotterill, I. C., et al. J. Chem. Soc. Perkin Trans. 1, 1991, 2505.
OBn
OH
O
O
O
1. h (350 nm)
O
Me
2. H2, Pd/C, PhH
O
Me
OH
OBn
O
O
OBn
OBn
OH
OH
84%
()-littoralisone
Mangion, I. K., MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 3696.

SPS Photochemistry

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SPS Photochemistry

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Physical Organic Photochemistry and

Basic Photochemical Transformations

X-rays and gamma-rays lead to ionization

UV/Vis for electronic absorption

IR for nuclear vibrational motion (IR)

Kasha's rule - relaxation to S1 is very rapid compared to other processes

Radiative decay to ground state (fluorescence or phosphorescence)

Photochemistry occurs from S1 (infrequent) or T1 states

Photochemistry occurs from S1 (infrequent) or T1 states

Allowed and Forbidden Processes

Spin forbidden transitions alter electron spin angular momentum

Allowed and Forbidden Processes

Spin forbidden transitions alter electron spin angular momentum

Bimolecular Photophysical Processes

Bimolecular Photophysical Processes

Bimolecular Photophysical Processes

Sensitizer should absorb at a different wavelength than acceptor molecule

Bimolecular Photophysical Processes

1/2 = 1/1 + kq[Q]

Description of quenching efficiency

Bimolecular Photophysical Processes

1/2 = 1/1 + kq[Q]

Description of quenching efficiency

Bimolecular Photophysical Processes

1/2 = 1/1 + kq[Q]

Description of quenching efficiency

# molecules that undergo a process

# molecules that undergo a process

Rate of photochemistry from S1 must outcompete fluorescence

Phosphorescence from T1 to S0 must be slow compared to photochemistry

Two or three energy surfaces are involved due to excited states

Three types of photochemical reaction diagrams

Small gap between surfaces promotes crossing

Small gap between surfaces promotes crossing

Transition to excited state, which has smaller energy barrier

Transition to excited state, which has smaller energy barrier

Tendencies of S and T states

Tendencies of S and T states

tend to have considerable zwitterionic character

tend to have biradical character

undergo rapid, concerted reactions

triplet state is longer lived

must compete with facile photophysical processes

Complete conversion to one isomer is difficult b/c both isomers absorb

Complete conversion to one isomer is difficult b/c both isomers absorb

(trans to cis) = 0.50

3-4 (impossible); 5 (difficult, reactive); 6-7 (facile, reactive); 8 or above (stable)

Hydrogen abstration is frequent in these reactions:

Hydrogen abstration is frequent in these reactions:

Six-membered H abstracted preferntially

Stereospecificity of singlet and triplet states - Example: disproportionation in Type II reactions

Alkene Hydrogen Abstraction

Alkene Hydrogen Abstraction

Alkene Hydrogen Abstraction

Alkene Hydrogen Abstraction

Norrish Type I Fragmentation

Several factor control rate of this -cleavage reaction

Norrish Type I Fragmentation

Several factor control rate of this -cleavage reaction

Norrish Type I Fragmentation

Norrish Type I Fragmentation

Norrish Type I Fragmentation

S1 [4 + 2] is not allowed by orbital symmetry, but radical T1 undergoes stepwise addition

Note that carbonyl/alkene [2 + 2]