Regioselectivity in nucleophilic addition of siloxyalkenes to an alkylideneallyl cation

被引：5

作者：

Fujita, Morifumi ^{[1
]}

Fujiwara, Koji ^{[1
]}

Okuyama, Tadashi ^{[1
]}

机构：

[1] Univ Hyogo, Himeji Inst Technol, Grad Sch Mat Sci, Kamigori, Hyogo 6781297, Japan

来源：

CHEMISTRY LETTERS | 2006年 / 35卷 / 04期

关键词：

D O I：

10.1246/cl.2006.382

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Alkylideneallyl cation generated from Lewis acid-mediated ring-opening reaction of alkylidenecyclopropanone acetal was employed for the reaction with siloxyalkenes to give [3 + 2] cycloaddition and acyclic addition products. All the products are the result of nucleophilic addition to the sp(2) center of the alkylideneallyl cation, and there is no sign of the nucleophilic addition to the sp center. The regioselectivity is independent of the electronic and steric effects of siloxyalkene nucleophiles, and is compatible with charge distribution of the allylic cation.

引用

页码：382 / 383

页数：2

共 9 条

[1]

Apeloig Y, 1997, DICOORDINATED CARBOC, P9

[2] Regioselective ring opening of alkylidenecyclopropanone silyl acetals [J].

Fujita, M ;

Fujiwara, K ;

Mouri, H ;

Kazekami, Y ;

Okuyama, T .

TETRAHEDRON LETTERS, 2004, 45 (43) :8023-8026

[3]

GROB CA, 1970, HELV CHIM ACTA, V53, P2119

[4] CATALYTIC ELECTROPHILIC REACTIONS OF CHRYSANTHEMIC ACID-DERIVATIVES WITH UNSATURATED ORGANOSILANES - AN APPLICATION TO SYNTHESIS OF MODIFIED TYPES OF C-15 AND C-20 ISOPRENOIDS WITH NON-HEAD-TO-TAIL LINKAGES [J].

OHNO, M ;

MATSUOKA, S ;

EGUCHI, S .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (24) :4553-4558

[5] LEWIS ACID-MEDIATED REACTION OF 2,2-DIALKOXYCYCLOPROPANECARBOXYLIC ESTERS WITH KETENE SILYL ACETALS - SYNTHESIS OF CYCLOPENTENONES [J].

SAIGO, K ;

SHIMADA, S ;

SHIBASAKI, T ;

HASEGAWA, M .

CHEMISTRY LETTERS, 1990, (07) :1093-1096

[6]

Siehl H.-U., 1997, DICOORDINATED CARBOC, P189

[7] STABLE VINYL CATIONS - DIRECT SPECTROSCOPIC OBSERVATION OF VINYL-SUBSTITUTED VINYL CATIONS [J].

SIEHL, HU ;

MAYR, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (03) :909-910

[8] Quantum chemical calculation of structures and NMR chemical shifts of substituted buta-1,3-dienyl-2-2-cations [J].

Siehl, HU ;

Brixner, S .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2004, 17 (11) :1039-1045

[9] NMR spectroscopic and quantum chemical characterization of the (E)- and (Z)- isomers of the penta-1,3-dienyl-2-cation [J].

Siehl, HU ;

Müller, T ;

Gauss, J .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2003, 16 (08) :577-581

← 1 →