Organic Photochemistry

Organic Photochemistry

Any chemical change bought about by light/electromagnetic radiation

Chemical Change : Any event in the molecular level after absorbing a photon.

No need for an overall chemical change

Wavelength range of e.m. radiation : 700-100nm (visible or uv)

Examples: Photosynthesis, vision etc.. Photosynthesis

Basic Steps in Photochemistry

Absorption of photon (with uv or light frequency) by a molecule takes it to an electronically excited state, which is the starting point for the subsequent reaction steps
Ground state: Electrons try to occupy the lowest possible orbitals in pairs Excited state: One electron occupy a higher energy orbital than the lowest energy level available for it

(overall energy of the molecule also increases)

An electronically excited species (finite life time only) may have different physical and chemical properties than the ground state. An electronically excited state is more energetic than the ground state and leads to more possibilities for the reaction The electronic configuration of excited state is more favorable for product formation

Chemical Processes by Excited Molecules

(A-B-C) (A-B-C) (A-B-C) (A-B-C) (A-B-C) RH (A-B-C) (A-B-C) A A-B. + C. E+ F Simple Cleavage Decomposition Intramolecular Rearrangement Photoisomerization Hydrogen Atom Abstraction Photodimerization Photosensitization

A-C-B A-B-C' A-B-C-H + R. (ABC)2 ABC + A*

Quantum Yield
A property relevant to most photo physical and photochemical processes A measure of efficiency with which absorbed radiation causes the molecule to undergo a specified change It is the number of product molecules formed for each quantum of light absorbed Definition: the number of moles of a stated reactant disappearing, or the number of moles of a stated product produced, per einstein of monochromatic light absorbed. (1 einstein = 1 mole of photons)

Jablonski Diagram

So + hv --- S1 S1v -- S1 + heat S1 ----- So + hv S1 ---- So + heat S1 --- T1 T1v -- T1 + heat T1v -- So + hv T1 --- So + heat S1 + A (So) --- So + A (S1) T1 + A (So) -- So + A (T1)

Excitation Vibrational Relaxation Fluorescence Internal Conversion Intersystem Crossing Vibrational Relaxation Phosphorescence Intersystem Crossing Singlet-Singlet Energy Transfer Triplet-Triplet Energy Transfer

Advantages of Photochemical Reactions

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

Drawbacks
Reactivity is often unpredictable Many substrates are not compatible Selectivity and conversion are sometimes low

Photosensitizor
Energy transfer through photosensitization
h D ISC 1D A + 3D 3A 3D D + 3A Products 1D D = Donor A = Acceptor 1 = Singlet 3 = Triplet

S1

S1 T1 74 Kcal .mole-1 S0 Benzophenone

ISC Energy transfer T1 69 Kcal/mole 120 Kcal/mole Butadiene h Ph2CO

1[Ph 2CO]

60 Kcal/mole S0

ISC

3[Ph

2CO]

3 Dimeric products

Ph2CO

Organic Photochemical reactions

I. Norrish Type-I Reactions ( -Cleavage)

Photochemistry of simple Ketones Step I -Cleavage

Step II Decarbonylation
Step III Recombination
O h R O C

The carbonyl group accepts a photon and is excited to a photochemical singlet state. Through intersystem crossing the triplet state can be obtained. On cleavage of the carbon carbon bond from either state, two radical fragments are obtained.

 The fragments can simply recombine to the original carbonyl compound (path A). By extrusion of carbon monoxide in path B, two organic residues can recombine with formation of a new carbon carbon bond When the carbon fragment has an -proton available it gets abstracted forming a ketene and a saturated hydrocarbon in path C When the alkyl fragment contains a -proton it gets abstracted with formation of an aldehyde and an alkene.

Norrish Type II reactions

Cleavage of 1,4-biradicals formed by -hydrogen abstraction The quantum yield for type II cleavage is only about 25%

III. Alkene isomerization (cis-trans isomerization)

Example: cis and trans stilbene.
Both cis and trans-stilbene undergo * electron excitation by absorption of uv light. A small proportion (6%) of the trans-S1 state fluoresces back to the trans-isomer. The stability of the stereoisomers of stilbene is due to a 62 kcal/mole barrier to rotation about the double bond produced by the -bond. This bonding is absent in the * excited state (magenta curve). These local S1 states quickly relax by means of non-radiative internal conversion to the transition state region of S0

h triplet donor

h 185 nm

h sens heat

IV. Di- methane rearrangement

V. Photoenolization

When the reactive carbonyl function and a -hydrogen are conjugated via an aromatic ring or double bond, the 1,4-diradical created by hydrogen abstraction quickly relaxes to a conjugated enol tautomer

If an aromatic ring has been disrupted by the photoenolization, the enoltautomer is unstable and rapidly reverts to the initial aromatic carbonyl compound. This might appear to be a useless transformation, but it finds practical application as a sunscreen ingredient

VI. Patern-Bchi Reaction (Photochemical synthesis of oxetans)

O O +

Paterno and Chieffi (1909), Buchi in 1954 mechanistic analysis

Reaction mechanism
ISC [PhCHO] S1

NH2
CHO

N O h O
[PhCHO] T1 (n-*)

N N

EtO

CO 2H

HO

O N

Kisc aromatic >> Kisc aliphatic (>>1010/s)

OH Thromboxane A2 responsible
O C C O C C

O Et Insecticidal activity O
C H

Oxetanocine

+
HN O
nucleophile

+
O OAc

OH

electrophile

Biradical intermediate O

O NH2 H 2N O Bradyoxetin
Major

OR
O

Merrilactone A

H OBz OAc Palitaxel

Minor

Intramolecular Paterno Buchi

O tBu
O

1.6

O h 1 atm O2
h O

tBu

+
O

tBu O O h, 11 atm O2 O O

h CHO

LAH O O OH

O Ph Ph

+
O
O O R

O Ph Ph C C
h

Ph O O lifetime = 1.6 nsO

O R

MeOH

O Ph OMe O
O

R OH