GLYCOSYLIDENE CARBENES .18. INSERTION OF GLYCOSYLIDENE CARBENES INTO THE SN-H BOND OF TRIBUTYLSTANNANE AND TRIPHENYLSTANNANE - A SYNTHESIS OF STANNOGLYCOSIDES

被引：14

作者：

UHLMANN, P ^{[1
]}

NANZ, D ^{[1
]}

BOZO, E ^{[1
]}

VASELLA, A ^{[1
]}

机构：

[1] ETH ZURICH,ORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND

来源：

HELVETICA CHIMICA ACTA | 1994年 / 77卷 / 05期

关键词：

D O I：

10.1002/hlca.19940770521

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Insertion of the glycosylidene carbenes, derived from the gluco- and the manno-diazirines 1 and 2, into the Sn-H bond of R(3)SnH (R = Bu or Ph) leads to the fully substituted stannoglycosides 3-8 (53-77%). The 1,2-cis-configurated products are formed preferentially (alpha-D/beta-D ranges from 2.5:1 to 5.1:1 with 1, and 1:1.3 to 1:4.2 with 2). Relative to CH2Cl2, THF favors formation of the equatorial Sn-glycosides. The stannylated (benzyloxy)glucals 9 and 10 were isolated as side products. The reaction of 1 with (Bu(3)Sn)(2) yielded 9 (17% in CH2Cl2; 36% in CCl4) together with the azines 11 and the benzyloxyglucal 12. NMR Data of the Sn-glycosides 3-8 show evidence for an anomeric effect, (1)J(C(1),H) being larger in the axial and (1)J(Sn,C(1)) larger in the equatorial anomers.

引用

页码：1430 / 1440

页数：11

共 45 条

[1]

BAX A, 1988, J MAGN RESON, V76, P569

[2] STUDY OF C-13H COUPLING-CONSTANTS IN HEXOPYRANOSES [J].