光敏反应 —— 光照条件下氧气的反应

Ren Lei 2009.12.12

1. 背景2. O2 的分类及产生的方法和机理3. 反应的类型 a 【 2+2 】环加成 b Ene 反应 c 【 4+2 】环加成 d N 参与的反应 e P 参与的反应 f S 参与的反应 g 其他反应

O2, hrO

O

Fritzsche Dufraisse,Windaus,Kautsky

Khan Foote and WexlerCorey and Tayloretc

Fritzsche, J. Compt. Rend. 1867, 64, 1035-1037

1867 1920s-1930s 1960s

主要是两种氧参与的反应1.Ground-state triplet O2 (Ground-state Molecular Oxygen)机理

2. Excited singlet 1O2

Chemical Reviews, 1971, Vol. 71, No. 4 395Photochemistry of Organic Compounds: From Concepts to Practice

hr 1(sens)* isc 3(sens)*3O2

sens + 1O2

alkrne Exciplex

O O

O O

H

O O

O

O

OOH

O

O

2+2

ene

4+2

【 2+2 】环加成

Tetrahedron Lett.1972,169-172

J.Am.Chem.Soc.2002,124,8814-8815Acc.Chem.Res. 2008, 41, 387-340

J.Am.Chem.Soc.2002,124,14004-14005Photochem.Photobiol.Sci.,2009,8,912--915

Ph

PhPh

Ph Ph

PhPh

Ph

O2 hrSens

O O O

Ph Ph

Org. Lett 2005 ,4265-4268

N

Acr -Mes

N

MeO

MeOhr

Rose Bengal ,O2

N

MeO

MeO

OO

N

MeO

MeO

O

O

Ph

o s o s

Pho o

Ph os

o

o

Tetrahedron 1980, 36,617¨C62

J.Org.Chem. 2002, 67,4937-4944

H

OX

H

OX

O

OXO O

OH

hr, TPFPP, O2

-100C

+

J.Am.Chem.Soc. 1999, 121, 1834-1838

MeO

hr ,Sensitzer

O26

6

33 O O

MeO

H

OO

MeO

MeO

O + CH3CHO

J.Org.Chem. 2000, 65, 6876-6878

R1 C R2

NOH hr ,Sensitizer,

O2R1 C N

R2

O O

OHR1 C R2

O+ HNO2

Rose Bengal J. 0rg. Chem., Vol. 41, No. 8, 1976

CA Org. Lett 2002 Vol.4,No.14 2325-2328

Platinum(II) Terpyridyl J.Org.Chem.2004,69,4788-4791Acetylide Complex

O2

TPP , hr , CCl4

OOO

n n

n>2

Org. Lett 2000 Vol.2,No.10 1383-1385

Ene 反应

Tetrahedron56(2000)9151¤C917

J.Am.Chem.Soc. 2000, 122, 7610-7611 J.Am.Chem.Soc. 2001, 123, 7228-7232

J.Org.Chem. 2008, 73,5606-5608

J.AM.CHEM.SOC.2007,129,4132-4133

hr O2sens octaacid

n nn=1,2,3

沸石

J.Am.Chem.Soc. 1996, 118, 10666-10667

【 4+2 】环加成

R

R1hr O2Sens

OO

R

R1

OO

Only activated aromatic compounds,such as benzenes with good electron-donating substituents or polycyclic aromatic hydrocarbons

O

R1

R1

R2

O

R1

R1

R2

OTPP O2 hr

CCl4

R2 CH2Ph ,CH2NPh< i-Pr< Ph

O

The first-time use of chiral-auxiliary-controlled1,3-dienes in [4 + 2] cycloaddition reactions with singlet oxygen

J.Am.Chem.Soc. 1998, 120, 4091- 4093

Pure Appl.Chem.2004,76 2105-2146

Actinometer

J.Am.Chem. Soc. 1995, 117,6439-6442

【 4+2 】 Natural Products

Acc.Chem.Res. 2008, 41, 1001-1011

OO

R1

HOStructure 1

OR1 SiR3

O2

hr Sens OO

O

SiR3

ROSiR3

O

OO

OH

R1

O

OO

R1

HO O OR1

Reduction

OR1

R2

OH

O2

hr Sens OO

O

R2

OH

R2CHO

Tetrahedron Lett.1981,22,3505-3508 J.Org.Chem. 2007,72,4826-4831

OO O

O O

R1 R2

Structure 2

OO O

O O

R1 R2

Ar

ArO

O

SiR3

R3Si

O2

hr ,SensAr

Ar

O

O

O

O

OH

HO

HO O

O O

R1 R2

HO

-H2O

J.Org.Chem. 1999,64,2680-2682 Org.Lett. 2005,7,2357-2359

Structure 3

LG

R1 OSiR3

LG

R1 OO

O2

hr ,Sens

OH

LG

R1 OO

OH

OO

GL

R1OOHOH

O O O O

R1

GL

OOH

OO O

GL OR1

O

KetalizationKetalization

O O O O

R1

GL

OO O

GL OR1

O

J.Org.Chem.1991 ， 56,960-969 ； Org.Lett.2007,9,5585-5588

O O R2O

n

Structure 4

OR1

OH

R2

n

n=1,2

OO

OH

R2

n

n=1,2

OH

R1=SiR3

Ketalization

1O2

1O2O

OO R2

n

OH

O O R2

R1

HOO

O O R2

Reduction

O

n

n

O O R2

R1

HOn

R1=H

Biosci.,Biotechnol.,Biochem.1992,56,1158-1159

J.Nat.Prod. 2006, 69, 1728-1733

OHO

R1

OH

R2

nm

m,n=1 or 2

O2

hr Sens O

OO

R2

OH

R1 OH

m

n

O OHOO

R1

OH R2

m

nOOO

R2R1

n mReduction

Ketalization

Structure 5O

OO

R2R1

n m

Org.Lett.2006,8,1945-1948

OR1 R2

OH

OR1 R2

OH

O2 ,ROHhr Sens O

OO R2

OH

R1 ROH

RO

OR1 R

2

OHRO OOH

OH

OO

R2

OHR1

OR2

O

R1

O

reduction

Structrue 6 OR2

O

R1

O

J.Nat.Prod.2004,67,2079-2082

J.Am.Chem.Soc. 2006, 128, 14685-14690

Tetrahedron:Asymmetry 2004, 15,259

N 的反应

N

OH

NO NO

major

O2 DCN hr

MV2+ MeCN

Angew. Chem. Inf. Ed. Engl. 1991.30,187

J.Am.Chem.Soc. 2004, 126,15956.

Org.Lett.2009,11,4568-4571

Ar

MeO

NHR

hr O2

TPP

Ar

MeO

NR

TL 1996, 37, 8189-8194

. J.Org.Chem. 2001, 66,4898

R3PO2

hr Sens R3P=O

J. Org. Chem., 1974 3178-3179

P 的反应

air rose bengal CH3CN

TiP2Te 1mol% hr Sens(RO)3P=O(RO)3P

Org.Lett.2009,8,1879-1881

S 的反应

S RRO2

hr SensS

OO

R

R S

OHO

R

R S

O

R

RO

S RR+ 3O2

S RR

S RR2

O

S RR

O

R'2 SO

R'SO2

Acc.Chem.Res.2001, 34,875-884

J.Am.Chem.Soc .2008, 130,4057 4068 4057

J.Phys.Chem.B 2006, 110, 2942 2948

S S S

+

OO O

O2

hr MOPDPP+

J.Am. Chem.Soc. 2004, 126,8914

Angew. Chem.,Int.Ed. 2004, 43,6532

O NHN COOH COO-

OOH

O

OHO2 hr TPP

L-AlanieDMSO RT 56%ee

Other reaction

CHO

CHO

hr O2

Sens CH2Cl2

hr O2

Sens CH2Cl2

N ClO4Org.Lett.2007,9,611-613

RoseBengal TetraphenylporphyrinMethylene Blue

NH

N N

HN

FF

F

F

F

FF

F

F

F

F

F

FF

FF

FF

F

F

TPFPP

O

BF4

TPP