THE SAMARIUM GRIGNARD REACTION - INSITU FORMATION AND REACTIONS OF PRIMARY AND SECONDARY ALKYLSAMARIUM(III) REAGENTS
THE SAMARIUM GRIGNARD REACTION - INSITU FORMATION AND REACTIONS OF PRIMARY AND SECONDARY ALKYLSAMARIUM(III) REAGENTS
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DOI：
10.1021/ja00041a024
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发表时间：
1992-07-15
影响因子：
15
通讯作者：
TOTLEBEN, MJ
中科院分区：
文献类型：
--
作者：
CURRAN, DP;TOTLEBEN, MJ
这项工作表明，伯自由基和仲自由基在 THF/HMPA 中迅速还原，形成伯烷基钐试剂和仲烷基钐试剂。伯自由基和仲自由基可以通过伯卤化物和仲卤化物的直接SMI2还原或通过先前的快速自由基环化形成。钐试剂在溶液中具有中等稳定性，并且它们与多种典型的亲电子试剂发生反应，包括醛和酮。该工作进一步表明，有机钐中间体可以参与在THF/HMPA中进行的醛和酮的传统钐Barbier反应。引入了一种称为“钐格氏法”的新程序，并且表明该新程序将比钐巴比尔反应具有更大的范围和通用性。
This work shows that primary and secondary radicals are rapidly reduced in THF/HMPA to form primary- and secondary-alkylsamarium reagents. The primary- and secondary-radicals can be formed either by direct SMI2 reduction of primary- and secondary-halides or by a previous rapid radical cyclization. The samarium reagents have moderate stability in solution, and they react with a variety of typical electrophiles, including aldehydes and ketones. The work further shows that organosamarium intermediates can be involved in the traditional samarium Barbier reaction of aldehydes and ketones conducted in THF/HMPA. A new procedure called the "samarium Grignard" method is introduced, and it is suggested that this new procedure will have considerably more scope and generality than the samarium Barbier reaction.