Clarification of the Reduction Behaver of Photoexcited Samarium Species and its Application to the Development of New Synthetic Process

它已经被揭示，其辐射具有可见光的辐射作用，可以降低Samarium diodide的能力。While the reduction of organic chlorides with SmI-D22-D2 alone is difficult， irradiation with visible light causes the efficient reduction of organic chlorides to the corresponding hydrocarbons。用可见光照射，用宝石二氯环丙烷进行非线性还原，用二硫代二苯二醇和苯二醇提供相应的环丙烷在良好的年份。The reaction may proceed via the hydrogen abstraction from PhSH by cycolopropyl radicals formed in situ by the reduction with SmI D22。一种新颖的光诱导减少了第16组异原子化合物的有机硒化、甲状腺素和碲化也得到了开发。在特定的、有机的selenides中，如果不能在黑暗中（或甚至在HMPA的存在）减少SmIIIIIIIIIIIIIIIIIIIIIIIIIIIID 22 D2-hv系统中有效地减少了SmIIIIIIIIIIIID 22 D2-hv系统。Moreover，烷基氯化物（R-Cl）与SmI-D22-D2在碳单氧化物（50大气压）中的光启动反应已被测试。reaction provides the corresponding asymmetManagement ketones （RC（=O）CH-D22-D2R） as a carbonylated product。A mManagement istic proposal includes the dimerization of acylsamarium species formed in situ by the reductive carbonylation of alkyl chlorides with CO and SmI-D22-D2。Irradiation with near-UV light dramatically also enhances the reducing ability of ytterbium diiodide （YbI-D22-D2）。有机基质、iodies、tosylates和telluries被YbI D22-hv系统有效地减少了，但当这些不能在黑暗中减少YbI D22-hv系统。

It has been revealed that the irradiation with visible light enhances the reducing ability of samarium diiodide. While the reduction of organic chlorides with SmIィイD22ィエD2 alone is difficult, irradiation with visible light causes the efficient reduction of organic chlorides to the corresponding hydrocarbons. Upon irradiation with visible light, gem-dichlorocyclopropanes undergo reductive dechlorination with samarium diiodide and benzenethiol to provide the corresponding cyclopropanes in good yields. The reaction may proceed via the hydrogen abstraction from PhSH by cycolopropyl radicals formed in situ by the reduction with SmIィイD22ィエD2. A novel photoinduced reduction of group 16 heteroatom compounds such as organic selenides, tosylates, and tellurides has also been developed. In particular, organic selenides, which can not be reduced with SmIィイD22ィエD2 in the dark (or even in the presence of HMPA), undergo reductive cleavage efficiently by using the SmIィイD22ィエD2-hv system. Moreover, the photoinitiated reaction of alkyl chlorides (R-Cl) with SmIィイD22ィエD2 in the presence of carbon monoxide (50 atm) is examined. The reaction provides the corresponding asymmetrical ketones (RC(=O)CHィイD22ィエD2R) as a carbonylated product. A mechanistic proposal includes the dimerization of acylsamarium species formed in situ by the reductive carbonylation of alkyl chlorides with CO and SmIィイD22ィエD2. Irradiation with near-UV light dramatically also enhances the reducing ability of ytterbium diiodide (YbIィイD22ィエD2). Organic bromides, iodies, tosylates, and tellurides are reduced efficiently by a YbIィイD22ィエD2-hv system, while these can not be reduced with YbIィイD22ィエD2 in the dark.