Organic Photochemistry

Introduction to Photochemistry
Classifications of Photochemical Reactions
Application of Photochemistry in Organic
Synthesis
Energies
100 kcal/mol= 4.3 eV= 286 nm= 35000 /cm (near UV)nano= 10-9
286 kcal/mol= 12.4 eV= 100 nm= 100000 /cm (far UV)
Typical Bond Energies

C-H = 110 kcal/mol

C-C = 80
C=C = 150
C=O = 170
Uv light 150 -40 nm wavelength, so this is sufficient energy to break bonds –knock
electrons out of bonding orbitals (electronic excitation).
 Chemically useful light is generally in the range of 200-400 nm
Often employ filters to regulate the wavelength of the radiation

π* π* π* π* π*

n n n n n

π π π π π

ground state (S0) n-π* (S1) n-π* (T1) π-π* (S1) π-π* (T1)
A Jablonski diagram, named after the Polish physicist AleksanderJabłoński, is a
diagram that illustrates the electronic states of a molecule and the transitions
between them.
The states are arranged vertically by energy and grouped horizontally by spin
multiplicity.
Radiative transitions are indicated by straight arrows and nonradiative transitions
by squiggly arrows.
The vibrational ground states of each electronic state are indicated with thick
lines, the higher rotational states with thinner lines.
 Physical Processes Undergone by Excited Molecules

• So + hv --- S1 Excitation
• S1v -- S1 + heat Vibrational Relaxation
• S1 ----- So + hv Fluorescence
• S1 ---- So + heat Internal Conversion
• S1 --- T1 Intersystem Crossing
• T1v -- T1 + heat Vibrational Relaxation
• T1v -- So + hv Phosphorescence
• T1 --- So + heat Intersystem Crossing
• S1 + A (So) --- So + A (S1) Singlet-Singlet Energy Transfer
• T1 + A (So) -- So + A (T1) Triplet-Triplet Energy Transfer
 Why Use Photochemistry

• Overcome large kinetic barriers in a short amount of time

• Produce immense molecular complexity in a single step
• Form thermodynamically disfavored products
• Allows reactivity that would otherwise be inaccessible by almost
any other synthetic method
• The reagent (light) is cheap, easily accessible, and renewable

• Drawback
• Reactivity is often unpredictable
• Many substrates are not compatible
• Selectivity and conversion are sometimes low
 Chemical Processes undergone by Excited Molecules

(A-B-C) A-B. + C. Simple Cleavage

(A-B-C) E+ F Decomposition

(A-B-C) A-C-B Intramolecular Rearrangement

(A-B-C) A-B-C' Photoisomerization

RH A-B-C-H + R.
(A-B-C) Hydrogen Atom Abstraction
(A-B-C) (ABC)2 Photodimerization
A
(A-B-C) ABC + A* Photosensitization
• 1) α-Cleavage (Norrish type I reaction). In solution the radicals undergo further reactions to give products.
• 2) Hydrogen Abstraction followed by cleavage = Norrishtype II
cleavage.The radicals can abstract a Hydrogen atom from a donor.
The resulting radicals can then undergo further reactions.
 Photodimerization

O O O

O O O O
hν (350 nm)
O + O O (1)
O O solvent O
1.0 M, 48 h
O O

4 12a 12b
• Photosensitization-This is an important alternative to direct excitation of
molecules, most commonly used as a way to create TRIPLET states that
are challenging to obtain directly. For example, Naphthalene has S1 108
kcal/mol above S0, and T1 62 kcal/mol above S0.Notice here S1and T1 a
re very different in energy, so very forbidden Intersystem crossing. Also
recall that we cannot go S to T on direction excitation.So how do we get
naphthalene into its T1excited state ?
• This T1 excited state will conveniently have the right amount
of extra energy, which it (3) can unload to the naphthalene
boosting it from S0to T1. If this causes the sensitizer to go
T1 to S0, then overall (naphthalene AND sensitizer) we
have conserved spin.
• We can add in a compound (sensitizer),which we can easily irradiate
and (1) excite into S1, which then (2) conveniently can ISC down to a
T1state.This T1excited state will conveniently have the right amount of
extra energy, which it (3) can unload to the naphthalene boosting it
from S0 to T1. If this causes the sensitizer to go T1to S0, then overall
(naphthalene AND sensitizer) we have conserved spin.
• 3) Cycloaddition
• Most people are familiar with:
• The allowed thermal (4+2) cycloaddition (Diels Alder), and
• The thermally forbidden (2+2) cycloaddition, and
• the photochemically allowed (2+2) cycloaddition.
• Carbonyls will undergo cycloadditions with alkenes under photochemical excitation (of
the carbonyl).
• The mechanism explains product formation, and also justifies the product ratio.
 R1
R2
O hν, (300 nm)
solvent
1a–f
R1 R2 R2
R1
+ O +
R2
O R1
2a–f 3f 4f

a b c d e f
R1 H CO2Et Ph H CO2Me Ph
R2 H H H CO2Et CO2Me Ph
 2a
O OH hν
+ + Equ. (4)
Ph O
1a 12
Ph O
13
 R1 R2
8
O
5
3a–f

R1 O O R1
2 R2
R
25a–f ODPM DPM 17a–f
1a–f
1 R2 R1
R2 R
O
20a–f O
28a–f
R2
R1 O
22a–f
 R1 R1 R1
R2 R2 R2
3a–f b O O 17a–f
O a

15 14 16

R1 R1 DPM R1 R1
R2 R2 R2 R2
25a–f O O ODPM 1a–f
ODPM O O 28a–f

DPM
24 23 26 27

R1 R1 R1
R2 R2 R2
20a–f O O O 22a–f

19 18 21
 CO2Me MeO2C CO Me
2
MeO2C
N N
hν
CN (2)
A–VE CN
N N
bridging
CN CN
4c 18 (95%)

A–VE = aryl–(diester) vinyl bridging

 MeO2C Pr Pr CO2Me
8 2
CO2Me
A–EV
7 1
bridging 5 N + N
CO2Me
Pr Pr
6 CN Pr N CN
MeO2C MeO2C N
N hν CN CN
CN 19 (20%) 20 (36%)
Pr N ADPM
path
CN Pr MeO2C Pr
4d
A–V
A–EV = aryl–(diester)vinyl MeO2C N + MeO2C
bridging N
bridging
A–V = aryl–vinyl bridging Pr N CN CN
MeO2C Pr N
CN CN
21 (16%) 22 (28%)
 19 (36%) 20 (20%)

CO2Me CO2Me CO2Me

Pr MeO2C Pr MeO2C Pr
MeO2C
b N N N
CN CN CN
Pr N Pr N Pr N
CN CN CN
45 46a 46b
A–EV
hν bridging
for R = Pr
CO2Me CO2Me CO2Me
MeO2C R MeO2C MeO2C
N N N
hν
CN CN CN 18 (95%)
R V–EV a
N N N
CN bridging
CN CN
R = H: 4c for R = H 43 44
R = Pr : 4d
for R = Pr
hν A–V
bridging
CO2Me CO2Me
CO2Me
Pr MeO2C Pr MeO2C
MeO2C Pr
c
N N
N
CN CN
Pr CN
Pr N N Pr N
CN CN CN
47 48a 48b

21 (16%) 22 (28%)
Syntheses of Natural Products
O N
O H MeO N
H H H H

H
CO2H
CO2H MeO2C OAr
Clerodane diterpenic acid Clerodane diterpenic acid
Synlett 1998, 912 Tetrahedron Lett. 1996, 37, 6869 (+)-Reserpine OMe
Chem. Commun. 1996, 1537
CO2Me
H

O OR1 (+)-Pallescensin B
Chem. Commun.
MeO2C H R' R OR2 1999, 117
O O
(+)-Forsythide aglucone dimethyl ester
Tetrahedron Lett. 1989, 30, 2255
HO
HO2C O

O
H
(+)-Eremopetasidone
H Org. Lett. 2001, 3, 263
(+)-Bilosespenes A and B
H H H O
Org. Lett. 2003, 24, 4741 H O

N O O
HH O HH H
(+)-3β-Angeloyloxy-
(+)-Capnellene (+)-Magellaninone furanoeremophilane
Angew. Chem. Int. Ed.
Pure Appl. Chem. Pure Appl. Chem.
2002, 41, 4090
2005, 7, 1221 2005, 7, 1221
Benzoquinones and their
Monoprotected Derivatives

O OMe
OMe
O O
o-Benzoquinone Masked o-Benzoquinone (MOB)

O O

O MeO OMe
p-Benzoquinone Masked p-Benzoquinone (MPB)
 Generation of Masked o-Benzoquinones

OMe OMe
[Oxidant]
R OR'
R
R'OH
OH O

Oxidant : TTN = Thallium(III) nitrate [Tl(NO3)3]

BTIB = Bis(trifluoroacetoxy)iodobenzene [PhI(OCOCF3)2]
DAIB = Diacetoxyiodobenzene [PhI(OAc)2]
 Self-dimerization of MOBs
O OMe
OMe
OMe O
OMe Diels-Alder
OMe + OMe
OMe
OMe
O
O

The formation of a dimer occurs via Diels-Alder reaction between two molecules of MOB

The reaction is highly siteselective

regioselective
stereoselective

Out of eight-possible isomers, only a single isomer is observed

Ref: 1) Anderson, G.; Berntsson, P. Acta Chem. Scand. B 1975, 29, 948.
2) Liao, C.-C.; Chu, C.-S.; Lee, T.-H.; Rao, P. D.; Ko, S.; Song. L.-D.; Shiao, H.-C.
J. Org. Chem. 1999, 64, 4102.
Dimerization (DI) vs Diels-Alder
Reaction (DA)
RateDI = kDI [MOB]2

RateDA = kDA [MOB] [Dienophile]

RateDI
= kDI X [MOB]
RateDA kDA [Dienophile]

MOB = Masked o-Benzoquinone

 Intermolecular Diels-Alder
Reactions of MOBs X

OMe
Rn OMe
O
X X
R
OMe
OMe R1 = R2 = CH3 X
OMe Rn OMe
X = CH2,
O
O O, NBz, S 1 2
R1 C60 R = R = CH3
=
R2
=
CH X = O, NH
3 1
OR
OMe DAIB
R OR2 O
R OMe
o
OH MeOH, 0 C O R1
= R2
=C
X H
3
H 3
2 =C
R X
OMe = CH R1 = R2 = CH3 O O
R 1 =
R CH CH2=CHX
OMe H
=C OMe
O
CH
2
+ Rn OMe
X
X
R OMe O
R OMe
O O
H
MeO OMe X = CHO, COMe, CO2CH3
Ph, OBn, SPh, SePh

Ref: Liao, C.-C.; Peddinti, R. K. Acc. Chem. Res. 2002, 35, 856.
 Intramolecular Diels-Alder
Reactions of MOBs ( )n
OX
( )n
OX
X

O + O
O
OMe OMe
OMe
OMe OMe
O
R1 = R2 = CH3 +
R3 = ( )n OX
X
R1 = CH3 H
n=1-3
X = H or TBS R2 = CH2CH=CHCH=CHX

R4 = H O
H OMe
O
R4
R1 = CH3 OR1
O R2 = CH2CH=CH2
OR2
R OMe O H
O R3 O OX . O
.
R1 = R2 = CH3 H BzO H
H R3 = H OBz
OX
R4 =

O X = TBS OX

H
4 eq. SmI2/-78 oC
OX THF/MeOH MeO OX MeO OX
MeO MeO
+
O O O

Ref: Liao, C.-C.; Peddinti, R. K. Acc. Chem. Res. 2002, 35, 856
Two Basic Rules:
1) Franck-Condon Principle
The absorption of light is very rapid (10-15secs duration), much faster than the rate for
atomic vibration, which means that the initial excited state will have the same geometry
as the ground state.
“At the instant of excitation, only the electrons are reorganized; the heavier nuclei retain
their ground state geometry”
The initial geometry of the excited state is seldom energy minimal –consequently
“something” is going to happen (vibrational cascade, fluorescence, reaction, ...etc.) after
absorption.
2) Electrons do not undergo spin inversion at the instant of excitation.
Inversion is forbidden by quantum mechanical selection rules, which requires
conservation of spin during excitation transitions. (Conservation of angular momentum).
Singlet to triplet transitions are called Inter System Crossing (ISC) and are formally
symmetry forbidden.
“some things are more forbidden than others”
There can be some grey area in the this area of “allowedness”.
Sometimes it is not “all or nothing”.
Often we talk about statistically likely or statistically unlikely / improbable ( but
not impossible).
Intersystem crossings CAN occur if the energy gap between S and T states is
small (their wavefunctions have some overlap).
This means there is more of an opportunity for the process to occur. But it is
still going to be a slow process.
This is more common in ketones and aromatics, but less common inalkenes
and dienes.
• The geometry of the excited state –after vibrational relaxation -is
usually different from the ground state.Simple example of ethene:Plot
of Dihedral angle between of the p orbitals (Φ) vs. Energy.For ethene,
in the ground state, lowest energy has Φ= 0 and 180o, maximum at 90o.
Then lets think about the excitation process...
• In alkenes, the electron excitation is πto π*.
• If the hv boosts one electron from πto π*, there are two possible outcomes:
• it forms a singletexcited state (so long as we obey conservation of spin –which we have to !)
• or
• it forms a tripletstate (changed spin of the electron during transition –forbidden)
• We call the ground state Soand the 1stexcited singlet state is S1.
• However, think about what the πbonding picture looks like now –there is no
overall πbonding. So now the lowest energy conformation of the “excited
ethene”has the CH2units perpendicular to minimize eclipsing interactions
(Φ= 90o) –and an energy maximum when the p orbitals are coplanar (Φ= 0
and 180o).This is a good example of:The geometry of the excited state –
after vibrational relaxation -is usually different from the ground
state.However there is something else to be aware of... HUND’S RULE.
• Hund's rule of Maximum Multiplicityis a principle (1925) of atomic chemistry
which states that a greater total spin state usually makes the resulting atom
morestable, most commonly manifested in a lower energy state, because it
forces the unpaired electrons to reside in different spatial orbitals.
• It has been shown that the actual reason behind the increased stability is a
decrease in the screening of electron-nuclear attractions. Total spin state is
calculated as the total number of unpaired electrons + 1.
• As a result of Hund's rule, constraints are placed on the way atomic orbitals
are filled using the Aufbau principle. Before any two electrons occupy an
orbital in a subshell, other orbitals in the same subshellmust first each
contain one electron.
• Also, the electrons filling a subshell will have parallel spin before the shell
starts filling up with the opposite spin electrons (after the first orbital gains a
second electron). As a result, when filling up atomic orbitals, the maximum
numberof unpaired electrons (and hence maximum total spin state) is
assured.
• Types of Excitation
• When an electron is excited, it usually goes into the lowest available vacant
orbital.
• For typical organic molecules, there are 4 possible type of electron excitation:
• 1) σ→σ*
• Common for alkanes or things that do not have lone pairs or πbonds.
• 2) n →σ*
• Common for amines, alcohols, ethers or things that have lone pairs but not
πbonds.
• 3) π→π*
• Common for alkenes, aldehydes, carboxylic acids, esters, or things that have
πbonds.
• 4) n →π*
• Common for aldehydes, ketones, esters, things that have lone pairs and πbonds.
• 1) σ→σ*
• 2) n →σ*
• 3) π→π*
• 4) n →π*
• These are listed in DECREASING energy. (Typically)
• The last two are by far the most important in organic
photochemistry.
• Almost all organic photochemistry is:
• π→π*
• orn →π*
• Most common examples are Alkenes undergoing π→π*, and
carbonyl compounds undergoing π→π* or n →π*
• The UV spectrum for ethene:This absorption of
UV irradiation is causing a π→π*
transition.Recall that Abs = εclε(absorption
coefficient) can be viewed as “allowedness”
• For acetone we see both π→π* and n →π* excitations.
• Notice
• a) the different energies required (longer λis lower energy)
• b) the different ε. The n →π* excitation is symmetry
forbidden –much lower ε.
• So n →π* takes less energy, but is forbidden / less likely.
• Summary and simplification of allowedness
• Selection rules tellus that whenthe TRANSITION
MOMENT INTEGRAL IS ZERO then a process is
forbidden.
• If it is not equal to zero, itis allowed.
• For electrons to move from one orbital to another, then
their wavefunctions must overlap.
• The more the wavefunctions overlap, the more allowed
the processis.
• So we can explain why π→π* is very allowed (large ε),
and n →π* less allowed (smaller ε).
• π→π* is very allowed (large ε), and n →π* less allowed (smaller ε).
• For electrons to move from one orbital to another, then their
wavefunctions must overlap.
• The more the wavefunctions overlap, the more allowed the
processis.
• The πand π*are in the same plane, and same areas in space,
therefore overlapping wavefunctions.
• The lone pairs are perpendicular to the πsystem, andhave little
overlap with π* and so smaller ε.
• Physical Processes
• When a molecules gets photochemically excited, it will not remain in
its excited state for long. (unstable)
• Most excitations are from the S0to S1states.
• Remember (S to T are forbidden)
• Promotions to S2or higher S states can and do occur, but these
states usually will quickly (around 10-12secs) drop to S1via
vibrational cascade and internal conversion. (Including collisions
with neighboring molecules).
• Therefore in most normal cases, the lowest vibrational level of S1is
the only important excited Singlet state to consider.
• There are 5 available physicalpathways open to this excited
molecule:
• 1) A molecule in the S1state can cascade down through the vibrational levels of
the S0state, and thus return to the ground state. It achieves this bygiving up its
energy in small increments to the environment. This process is called INTERNAL
CONVERSION (IC). This is usually a slow process, and is not a preferred
pathway.This is an example of radiationless transition, or nonradiative decay.
• 2) A molecule in the S1state can drop to some low vibrational level of the S0state by giving
off the energy in the form of light. (radiative transition)
• This is a relatively
• slow process (10-9secs).
• This is called
• FLUORESCENCE.
• This is called FLUORESCENCE.
• This process is also not that preferred as it can be slow, and other
things can happen before fluorescence has the time to occur.
• It is more common in small (diatomic) or rigid (aromatic) molecules.
• Since the decay is to some low vibrational level of the S0state, the
hv emitted is of lower energythat that which was put in.
• I.e. Fluorescence gives out a longer λthan was used to excite.
• S →S transition is called fluorescence(allowed –faster 10-9s)
• T →S transition is called phosphorescence(less allowed –slower 10-
3s)
• 3) It is possible for some (but not necessarily all) molecules in the
S1state to undergoan INTERSYSTEM CROSSING (ISC) to the
lowest energy triplet state T1.
• 3) It is possible for some (but not necessarily all) molecules in the
S1state to undergoan INTERSYSTEM CROSSING (ISC) to the lowest
energy triplet stateT1.
• Formally S to T transitions are forbidden (conservation of angular
momentum!), but some are more forbidden than others!
• ISC is less forbidden when the S and T states are of similar energy
(their wavefunctions have some overlap).
• More common in carbonyl and/or aromatic systems. Less so in alkene,
diene type compounds.
• ISC occurs without loss of energy.
• Since the excited singlet state is higher in energy than the
corresponding triplet state (Hund’s Rule), there will be excess energy
that has to be given up.
• The most common pathway is to ISC to a T1state in a high vibrational
level, and then have T1to cascade down to its lowest T1level.
• This cascade can be fast (10-12s).
• 4) A molecule in the T1statemay return to the S0state by either emitting:
• heat
• (actually ISC to S0in a higher
• vibrational state and then
• vibrational cascade).
• or
• light
• (this radiative process is called
• PHOSPHORESCENCE).
• Since both these involve an
• ISC, they are relatively slow
• (10-3to 101sec) –because of
• their forbidden-ness.
• T1states therefore tend to
• have longer lifetimes than S1
• states.
• 5) If nothing else initially happens to the excited
molecule, then a molecule in its S1or T1state can transfer
its excess energy to another molecule.
• E.g. Just as in photosensitization described earlier.
• Photochemistry
• For Carbonyl Compounds, there are 3 common
types of photochemical reaction:
• 1) αCleavage (Norrish type I reaction)
• 2) Hydrogen Abstraction (can be followed by
Norrishtype II cleavage)
• 3) Cycloaddition
• Carbonyl compounds when irradiated can
undergo cleavage of the Carbonyl C -αbond.In
the gas phase the radicals are generated and
detected (longerlifetime).
• arrowsHere we have a bit of a problem, because you cannot
write an accurate Lewis structure to represent an excited
state.Even though it is convenient to write the diradical form,
with the πbond broken, it is not accurate, really one of the
lone pair electrons is promoted to the π*, if [n, π*]
• So when we write this type of mechanism, the cleavage is a two
step process.
• You can get further reactions after the cleavage.
• 2) Hydrogen Abstraction Theradicals can abstract a Hydrogen
atom from a donor. The resulting radicals can then undergo
further reactions. (Likedimerization).E.g. Photopinacolization.