Kimura Tsutomu, Sekiguchi Koto, Ando Akane, Imafuji Aki
Department of Chemistry, Graduate School of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Beilstein J Org Chem. 2021 May 28;17:1352-1359. doi: 10.3762/bjoc.17.94. eCollection 2021.
A series of 1-heteroatom-substituted vinyl -tolyl sulfoxides were prepared and treated with organometallic reagents to evaluate which combination of sulfoxides and organometallic reagents yielded alkynes the most efficiently. The use of 1-chlorovinyl -tolyl sulfoxide and isopropylmagnesium chloride was optimal for this purpose. A variety of 1-chlorovinyl -tolyl sulfoxides were prepared from carbonyl compounds and chloromethyl -tolyl sulfoxide and were converted into alkynes via the sulfoxide/magnesium exchange reaction and subsequent Fritsch-Buttenberg-Wiechell (FBW) rearrangement of the resulting magnesium alkylidene carbenoids. The mechanism of the FBW rearrangement of magnesium alkylidene carbenoids was studied by using C-labeled sulfoxides and by using DFT calculations.
制备了一系列1-杂原子取代的乙烯基-甲苯基亚砜，并与有机金属试剂反应，以评估亚砜和有机金属试剂的哪种组合能最有效地生成炔烃。为此，使用1-氯乙烯基-甲苯基亚砜和异丙基氯化镁最为合适。多种1-氯乙烯基-甲苯基亚砜由羰基化合物和氯甲基-甲苯基亚砜制备而成，并通过亚砜/镁交换反应以及所得亚烷基镁类卡宾随后的弗里茨希-布滕贝格-维歇尔（FBW）重排反应转化为炔烃。通过使用碳-标记的亚砜以及密度泛函理论（DFT）计算研究了亚烷基镁类卡宾的FBW重排反应机理。
