DIRECT MICHAEL-TYPE ADDITION OF SI-GROUPS TO ALPHA,BETA-UNSATURATED BETA-ARYL-SUBSTITUTED ENONES WITH R3SICL/BU2CU(CN)LI2

被引：23

作者：

AMBERG, W ^{[1
]}

SEEBACH, D ^{[1
]}

机构：

[1] SWISS FED INST TECHNOL,ORGAN CHEM LAB,UNIV STR 16,CH-8092 ZURICH,SWITZERLAND

来源：

CHEMISCHE BERICHTE | 1990年 / 123卷 / 12期

关键词：

MICHAEL ADDITION OF SI GROUPS; CUPRATES; HIGHER-ORDER; KETONES; BETA-ARYL BETA-SILYL;

D O I：

10.1002/cber.19901231227

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(E)-5-Benzylidene-2-tert-butyl-6-methyl-1,3-dioxan-4-one (1) undergoes conjugative silylation (Me3Si, Et3Si, tBuMe2Si, Me2PhSi, products 2-5) with the reagent specified in the title. The reaction is highly diastereoselective, with formal anti addition of R3Si and H from the Re- and Si-face, respectively, of the exocyclic double bond [proof by NMR analysis and chemical correlation (cf. 6 and 7)]. A screening of various enone systems showed that this unprecedented Michael addition of Si groups with chlorosilane as a reagent, and under non-reducing conditions occurs only if the alpha,beta-unsaturated carbonyl system bears an aryl group in the beta-position to give beta-aryl beta-silyl ketones (products 8-15).

引用

页码：2439 / 2444

页数：6

共 29 条

[21]

HUNIG S, 1979, INTEGRIERTES ORGANIS, P440

[22]

LIPSHUTZ B, 1990, J AM CHEM SOC, V112, P4031

[23]

LIPSHUTZ BH, 1990, SYNLETT, P119

[24] SYNTHESIS OF SUBSTITUTED CYCLOHEXENONES [J].

NOVELLO, FC ;

CHRISTY, ME ;

SPRAGUE, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1953, 75 (06) :1330-1334

[25] AN ALKALOID OF DIOSCOREA HISPIDA, DENNSTEDT .1. THE LACTONE RING [J].

PINDER, AR .

JOURNAL OF THE CHEMICAL SOCIETY, 1952, (JUN) :2236-2240

[26]

PINDER AR, 1952, J CHEM SOC, P2240

[27]

Posner G. H., 1980, INTRO SYNTHESIS USIN

[28]

TIETZE LF, 1981, REAKTIONEN SYNTHESEN, P159

[29]

WATTANASIN S, 1980, SYNTHESIS-STUTTGART, P647

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