Regio- and stereochemistry on the electrophilic trapping of allylic samariums generated by reductive cleavage of allylic ethers with (C5Me5)2Sm(thf)n

被引：23

作者：

Takaki, K ^{[1
]}

Kusudo, T

Uebori, S

Nishiyama, T

Kamata, T

Yokoyama, M

Takehira, K

Makioka, Y

Fujiwara, Y

机构：

[1] Hiroshima Univ, Fac Engn, Dept Appl Chem, Higashihiroshima 7398527, Japan

[2] Kyushu Univ, Grad Sch Engn, Dept Chem & Biochem, Higashi Ku, Fukuoka 8128581, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 13期

关键词：

D O I：

10.1021/jo9723016

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The C-O bond of allylic benzyl ethers was selectively cleaved with Cp-2*Sm(thf)(n) to give allylic samarium complexes in good yields. Facility of their bond fission has been found to be comparable to that of the corresponding propargylic ethers intermolecularly, but lower intramolecularly. Regio- and stereochemistry on the electrophilic trapping of the allylic complexes thus generated remarkably depended on the nature of the electrophiles. They reacted with carbonyl compounds exclusively from the most substituted terminus of the allylic moieties to yield blanched homoallylic alcohols with anti diasteroselectivity. On the other hand, trapping with silyl chlorides produced linear allylic silanes. Here, a plausible mechanism to account for the difference is proposed.

引用

页码：4299 / 4304

页数：6

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