Samarium(II) triflate as a new reagent for the Grignard-type carbonyl addition reaction

被引：42

作者：

Fukuzawa, S ^{[1
]}

Mutoh, K ^{[1
]}

Tsuchimoto, T ^{[1
]}

Hiyama, T ^{[1
]}

机构：

[1] TOKYO INST TECHNOL,RESOURCES UTILIZAT RES LAB,MIDORI KU,YOKOHAMA,KANAGAWA 226,JAPAN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1996年 / 61卷 / 16期

关键词：

D O I：

10.1021/jo960260s

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

On treatment of a THF solution of Sm(OTf)(3) with 1 equiv of an organolithium or organomagnesium reagent-at ambient temperature, the purple or deep green solution of the divalent samarium triflate [Sm(OTf)(2)] was readily obtained. For this preparation, s-BuLi was the most effective as was evidenced by the reduction of a-phenylethyl iodide in the presence of HMPA. The Sm(OTf)(2) reagent mediated the Grignard-type reaction effectively in THF/HMPA; alkylation and allylation of ketones or aldehydes with alkyl, allyl, or benzyl halides proceeded via organosamarium intermediates. Diastereoselectivity of the samarium-Grignard reaction was examined using 2-methylcyclohexanone, 4-tert-butylcyclohexanone, and 2-phenylpropanal and was found to be higher in each case than that with SmI2. With 2-methylcyclohexanone, for example, Sm(OTf)(2) gave the greatest ratio of axial alcohol:equatorial alcohol = 99:1, and SmI2 gave a ratio of 91:9. Halides containing an ester or a silyl group were reactive in the Reformatsky- or Peterson-type reaction, respectively, using the Sm(OTf)(2) reagent.

引用

页码：5400 / 5405

页数：6

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