Stereoselectivity of triplet photocycloadditions: Diene-carbonyl reactions and solvent effects

被引：64

作者：

Griesbeck, AG ^{[1
]}

Buhr, S ^{[1
]}

Fiege, M ^{[1
]}

Schmickler, H ^{[1
]}

Lex, J ^{[1
]}

机构：

[1] Univ Cologne, Inst Organ Chem, D-50939 Cologne, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 12期

关键词：

D O I：

10.1021/jo971767l

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The diastereoselectivity of the photocycloaddition of benzaldehyde to furan was determined (exo/endo = 212:1) and compared with the reaction of other carbonyl compounds and carbonyl analogues. These results were compared with Paterno-Buchi reactions of cycloalkenes and cyclic enol ethers. An increase in steric demand of the a-substituent in benzoyl compounds led to a change in exo/endo-selectivity for furan cycloadditions that was not observed for cycloalkenes or cyclic enol ethers. Different ISC-reactive conformers with enhanced spin-orbit coupling are postulated as a reasonable explanation for the stereoselectivities observed. Additionally, solvent effects were studied, demonstrating the influence of photoinduced electron-transfer steps on the regio- and diastereoselectivity of Paterno-Buchi reactions with 2,3-dihydrofuran in polar solvents. Two bicyclic oxetanes (8 and 10) were characterized by X-ray structure analysis.

引用

页码：3847 / 3854

页数：8

共 80 条

[1]

[Anonymous], 1991, COMPREHENSIVE ORGANI

[2]

Bartolotti L.J., 1996, REV COMP CHEM, V7, P187, DOI [10.1002/9780470125847.ch4, DOI 10.1002/9780470125847.CH4]

[3] Electronic control of stereoselectivity in photocycloaddition reactions .7. Stereoselectivity in the Paterno-Buchi reaction of 2,2-diisopropyl-1,3-dioxol with methyl trimethylpyruvate [J].

Buhr, S ;

Griesbeck, AG ;

Lex, J ;

Mattay, J ;

Schroer, J .

TETRAHEDRON LETTERS, 1996, 37 (08) :1195-1196

[4] CHIRAL INDUCTION IN PHOTOCHEMICAL-REACTIONS .10. THE PRINCIPLE OF ISOINVERSION - A MODEL OF STEREOSELECTION DEVELOPED FROM THE DIASTEREOSELECTIVITY OF THE PATERNO-BUCHI REACTION [J].

BUSCHMANN, H ;

SCHARF, HD ;

HOFFMANN, N ;

PLATH, MW ;

RUNSINK, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (14) :5367-5373

[5]

CALDWELL RA, 1989, KINETICS SPECTROSCOP, P77

[6] PHOTOCHEMICAL 2+2 CYCLO-ADDITION OF ARENECARBOXYLIC ACID-ESTERS TO FURANS AND 1,3-DIENES - 2+2 CYCLOREVERSION OF OXETANES TO DIENOL ESTERS AND KETONES [J].

CANTRELL, TS ;

ALLEN, AC ;

ZIFFER, H .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (01) :140-145

[7] SPIN-ORBIT-COUPLING IN BIRADICALS - ABINITIO MCSCF CALCULATIONS ON TRIMETHYLENE AND THE METHYL METHYL RADICAL PAIR [J].

CARLACCI, L ;

DOUBLEDAY, C ;

FURLANI, TR ;

KING, HF ;

MCIVER, JW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (18) :5323-5329

[8]

Carless H. A. J., 1984, SYNTHETIC ORGANIC PH, P425

[9] HIGHLY REGIOSELECTIVE [2 + 2] PHOTOCYCLOADDITION OF AROMATIC-ALDEHYDES TO ACETYLFURANS [J].

CARLESS, HAJ ;

HALFHIDE, AFE .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1992, (09) :1081-1082

[10] DYNAMICS OF FLEXIBLE TRIPLET BIRADICALS [J].

DOUBLEDAY, C ;

TURRO, NJ ;

WANG, JF .

ACCOUNTS OF CHEMICAL RESEARCH, 1989, 22 (06) :199-205

← 1 2 3 4 5 6 7 8 →