Reactions of an Isolable Dialkylstannylene with Propynoates and Benzyne

Reactions of an Isolable Dialkylstannylene with Propynoates and Benzyne
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可分离的二烷基亚锡与丙酸酯和苯炔的反应

DOI:
10.1021/acs.organomet.8b00197
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发表时间:
2018-07
期刊:
影响因子:
2.8
通讯作者:
Kira Mitsuo
Kira Mitsuo
中科院分区:
化学2区
文献类型:
--
作者:
Xu Jian;Xiao Xu-Qiong;Yan Chenting;Li Zhifang;Lu Qiong;Yang Qian;Lai Guoqiao;Kira Mitsuo

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稳定的单体二烷基亚锡烷基1与甲基和乙基丙炔酸酯的反应得到相应的1:2加合物,烯基(炔基)锡烷2和3在高产率,而1不与母体乙炔或常见的单-和二取代的乙炔,如苯乙炔,三甲基甲硅烷基乙炔,二乙基2-丁炔二酸酯等反应。值得注意的是,2和3具有Z-构型的烯基部分,在对比由已知的甲硅烷基与末端乙炔反应得到的类似加合物。结果表明,羰基氧配位环状两性环的形成是反应的关键中间体。亚锡基1加成到原位生成的苯炔上,形成具有独特的3-锡-1-硅茚满环体系的1:1加合物。
The reactions of stable monomeric dialkylstannylene 1 with methyl and ethyl propynoates give the corresponding 1:2 adducts, alkenyl(alkynyl)stannane 2 and 3 in high yields, while 1 does not react with parent acetylene or common mono- and disubstituted acetylenes such as phenylacetylene, trimethylsilylacetylene, diethyl 2-butynedioate, etc. Notably, 2 and 3 have the Z-configuration of the alkenyl moieties, in contrast to similar adducts obtained by the known reactions of silylenes with terminal acetylenes. It is suggested that the formation of a carbonyl oxygen-coordinate cyclic zwitterion as a key intermediate is essential for the reactions. Stannylene 1 adds to in situ generated benzyne, forming a 1:1 adduct having a unique 3-stanna-1-silaindane ring system.
将可分离的二烷基亚锡插入到酰氯的 C-Cl 键中,得到酰基(氯)锡烷
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期刊: Organometallics
影响因子: 2.8
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