Nishii Yoshinori, Nagano Takao, Gotoh Hideki, Nagase Ryohei, Motoyoshiya Jiro, Aoyama Hiromu, Tanabe Yoo
Department of Chemistry, Faculty of Textile Science and Technology, Shinshu University, Ueda, Nagano 386-8567, Japan.
Org Lett. 2007 Feb 15;9(4):563-6. doi: 10.1021/ol062673d.
A couple of radical carbonylations of gem-dihalocyclopropanes 1 using CO and Bu3SnH (formylation) or Bu3Sn(CH2CH=CH2) (allylacylation) successfully proceeded to give trans and cis adducts (2 and 3) with good to excellent stereoselectivity (trans/cis = >99/1-75/25 or 17/83-1/99). The formylation of 2,3-cis-disubstituted 1,1-dihalocyclopropanes enhanced trans selectivity (trans/cis = >99/1-95/5), whereas both 2,3-cis-disubstituted and 2-monosubstituted 1,1-dihalocyclopropanes underwent allylacylation with nearly complete trans selectivity (trans/cis = >99/1). Inherently less reactive gem-dichloro- and bromochlorocyclopropanes than gem-dibromocyclopropanes served as favorable substrates. [reaction: see text].
使用一氧化碳和三丁基氢化锡（甲酰化反应）或三丁基锡（2-丙烯基）（烯丙基酰化反应）对偕二卤代环丙烷1进行的几个自由基羰基化反应成功进行，得到具有良好至优异立体选择性的反式和顺式加合物（2和3）（反式/顺式 = >99/1至75/25或17/83至1/99）。2,3-顺式二取代的1,1-二卤代环丙烷的甲酰化反应提高了反式选择性（反式/顺式 = >99/1至95/5），而2,3-顺式二取代和2-单取代的1,1-二卤代环丙烷均以几乎完全的反式选择性进行烯丙基酰化反应（反式/顺式 = >99/1）。与偕二溴环丙烷相比，固有反应活性较低的偕二氯环丙烷和溴氯环丙烷是有利的底物。[反应：见正文]
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