[Link].

Semester-IV
Core Course-9 (CC-9)
Synthetic Organic Chemistry

III. Photochemistry
5. Arene-Alkene Photocycloaddition Reaction

Dr. Rajeev Ranjan

University Department of Chemistry
Dr. Shyama Prasad Mukherjee University, Ranchi
III Photochemistry 10 Hrs
Thermal versus photochemical reactions, Electronic excitations: n–π* and π–π* transitions. Singlet
and Triplet energy states: Comparison of energies, Lifetimes and Reactivity. Jablonski diagram,
Allowed and forbidden transitions: Fluorescence, Phosphorescence and Internal conversion and
Intersystem crossing.
Photochemical reactions of saturated ketones : Norrish Type I and Norrish Type II reaction,
Photoreduction of ketone, Photoaddition reactions, Paterno Buchi reaction. Photochemistry of
simple olefins : Cis-trans isomerization, Di-pi methane rearrangement. Photooxidation : Formation
of peroxy compounds, oxidative couplings : Barton reaction. Photo rearrangements : Photo-Fries
rearrangement and Photo rearrangement of 2,5-Cyclohexadienones.

Coverage:
Arene-Alkene Photocycloaddition Reaction

2
 Arene-Alkene Photocycloaddition Reaction

3
Dr. Rajeev Ranjan
 Arene-Alkene Photocycloaddition Reaction

1 1
1
6 2

3
2 5
4 4
ortho
+ para

meta

Possible modes of addition in the arene-alkene photocycloaddition reactions

4
Dr. Rajeev Ranjan
 6
meta cycloaddition C C
(3C + 2C) 1
C 2 C

prefulvene 6
C* 
+

*
6 - 2
3
C 5 1

4 2
C

Dr. Rajeev Ranjan

3
+ Exciplex

para cycloaddition
C* C*

C C
(2C + 2C)

(4C + 2C) ortho cycloaddition

Mechanistic proposal for the arene-alkene photocycloaddition reaction 5

 6
Dr. Rajeev Ranjan
 7
Dr. Rajeev Ranjan
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Dr. Rajeev Ranjan
 CN CN
CN h
+ +
2
5

C C C C

O O
O O

z
O z z
O O
O
z = OMe
z = CONH2, CN, Me
9
Dr. Rajeev Ranjan
 C
C
R

-a

b
R
a c C C
+
R
R -b R

R
R

-ac

C C
R

R
C

Possible mode of cleavage of the cyclophotoadduct

10
Dr. Rajeev Ranjan
 R
H R
h H
+ R

endo exciplex

11
Dr. Rajeev Ranjan
 O h
+ secondary orbital intercation is not favored
O
O due to presence of non bonded "O" electron
O

exo adduct

O
O O
O O
h O
+ O +
O

endo exo
5 1



*


12
Dr. Rajeev Ranjan
 11

C 10 2
8 h 1
2 C 3
7 1 7
3
6 5 4
6 4
5
Favored

3
8 11
2 C
1 10 2
C 1
4 3
6
5 7
Disfavored 6 5 4

Isocomene

Br Li, CuI Li
+ +
Li, NH3
Br
O O

Tetrahedron, 1981, 37, 4445

13
Dr. Rajeev Ranjan
 vs. h

OMe
OMe OMe
exo
endo

H OMe
OMe

favored
disfavored

O Li, Et2O
+
Br Li, NH3
OMe OMe

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Dr. Rajeev Ranjan
 Allylic stereocontrol: for the synthesis of silphiperfolene

Me Me
h
Me vs Me
H
Me H
Me
H Me

disfavored favored

h, CH3CHO

H H
O O H
HO
Me OH Me Me

PhNO2SeCN
Bu3P
H 2 O2

Li, NH3(l)
H

Me H

Silphiperfolene Me

Tet. Lett, 1985, 26, 5987 15

Dr. Rajeev Ranjan
 6 5 11 11
7 5 4
10 h
1
3
8 4 OAc
1 9
2 3 2
OAc 9
Modhephene

H H

H CO2 H
hirsutene
-cedrene retigeranic acid
O

O H HO2 C
O
O
O
O O H
OH
3-oxosilphinene subergorgic acid
isoiridomyrmecin coriolin

HO JACS, 103, 688, 1981

OH
O [Link], 23, 3983, 1982
ibid, 31, 2517, 1990
O ibid, 24, 4543, 1983
ibid, 24, 5325, 1983
ibid, 31, 5429, 1990
rudmollin ibid, 27, 1986, 1857.
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Dr. Rajeev Ranjan
 O Li, Et2O C*
h
+
NH3 C*
Br

Li, NH3

Silphene

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Dr. Rajeev Ranjan
 h C LAH
+ OAc OAc
O
OAc C MnO2

Me Me Me Me
LDA, -780C Me2CuLi, THF

MeI
O
(Me2N)2POCl
OR + OR
Me

H2, PtO2

Me
O3, MeOH O NaBH3CN
OR
NaBH4 O
Me Me
OMe

O
Me
Iso iridomyrmecin

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Dr. Rajeev Ranjan
 CHO

NH3+ O3, DMS OH

+
CO2-
CHO CHO

Br O O
Zn(BH4)2
TsCl, PCC O NBS, AIBN H2, Pt
O KOH

OTs
OTs
O O
O O O O O OH
LDA, DMPU
h

O
Li, MeNH2 O P NMe2 Li, EtNH2
O
NMe2
KHMDS Me2N P O
(Me2N)2POCl NMe2
Laurenene
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Dr. Rajeev Ranjan
 h C
h
C
HCONH2

OHC +
C*
H2 NOC H2 NOC CO2 H
C*

4+2
HO2 C R2 NOC
R2 NOC

Retigeranic acid
(Ph3P)3RhCl, H2
Br2, AcOH
O KOH

CO2 H
Ph3P+CH3Br-,
nBuLi

(-)-Carvone 20
Dr. Rajeev Ranjan
 Li, Et2O PCC
h, 3C + 2C
Br CHO EGC/CSA
O
OH O

C (PhCO)2O, h
K, 18-C-6
C NC O
O O CH3CN
O
O O

OH
O Cl
mCPBA LICA, THF SOCl2
O O O

O O O
O

HO
NaClO2 HO2 C

O O

Subergorgic acid
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Dr. Rajeev Ranjan
 Seven membered ring synthesis based on arene-olefin cycloaddition

OMe OMe
H H
h, 3C+ 2C Hg(OAc)2
OH O
OTBS
OH
THF, H2O
OTBS OTBS

NaBH4
MnO2,H2 H H
H
(PhCO)2O OR MsCl, Pyr
OR
O OH
KHMDS, allyl-I LAH, Heat
OTBS OTBS OTBS
OBn
OTBS OTBS

H
H H

O O
O
OBn CO2 H O HO
OBn O O
OH

O
HO
OH O
Tet. Lett, 1986, 27, 1857
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Rudmollin Dr. Rajeev Ranjan
 OAc OAc
OMe OAc OMe
OTBS OMe OTBS
h
OTBS
C C

OAc PhSeCl
OMe
OTBS C*
OAc OAc
C* H
H

OTBS OTBS
OTBS Cl
O O
O Cl

KOH

O
O H
H OH OTBS H
HO
OH H OMe OAcOTBS OMe OAc
OTBS
OTBS OH
OH
O Grayanotoxin

Disfavored Favored

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Dr. Rajeev Ranjan
 COX
COX R R ClOC
h R
R R
R

X = OMe, R = Me

O
O
COCHN2
R
R
R
R

Fenestrane derivative

Tetrahedron, 1985, 41, 5697

24
Dr. Rajeev Ranjan
 OMe
OMe
C OMe

+ .
X
X
X
X OMe
Si-face of olefin in exo-adduct
(Re-face in endo-adduct)

Introduction OMe
of PD tether C
OMe
.
X

X
X OMe
Re-face of olefin in exo-adduct
* *
O O (Si-face in endo-adduct)
6-substituted 7-substituted

O O
O OH OEt O O

Hg(OAc)2

OH
HO OH O O
O OH
+

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Dr. Rajeev Ranjan
 O Rn Rn O

O O O O
O
O
2R + + 2S

O O O O
O O
O O

Rn Rn
Si- face attack to the olefin Re- face attack to the olefin

Stereochemistry at 2- position is important

Abolished stereochemistry at C-2

O O
C C Abolished stereochemistry at C-4 O
O O C
C C
O
C
Re-face Re-face

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Dr. Rajeev Ranjan
 MeO MeO MeO

OMe CuCN
9-BBN

MgBr Cy-hex-2-enone DMP H

MeLi, allyl-I
L-selectride OH OTBS O OTBS

MeO OMe
MeO MeO

MeO
OTBS
OH OTBS OH
OTBS
endo (favored)
exo ( disfavored)

OH
HO

HO
H H
OH
aphidicolin stemodinone 27
Dr. Rajeev Ranjan
 Thank You

Dr. Rajeev Ranjan

University Department of Chemistry
Dr. Shyama Prasad Mukherjee University, Ranchi

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