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首页> 外文期刊>Chemistry: A European journal >Rhodium(I)-catalyzed intramolecular carbonylative [2+2+1] cycloadditions and cycloisomerizations of bis(sulfonylallene)s
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Rhodium(I)-catalyzed intramolecular carbonylative [2+2+1] cycloadditions and cycloisomerizations of bis(sulfonylallene)s

机译：铑（I）催化的双（磺酰基丙烯烯）分子内羰基化[2 + 2 + 1]环加成和环异构化

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摘要

Novel [{RhCl(CO)dppp}_2]catalyzed intramolecular carbonylative [2+2+1] cycloadditions of bis(phenylsulfonylallene) derivatives under CO, leading to the facile formation of bis(phenylsulfonyl)bicyclo[n.3.0] frameworks (n=4-6), have been developed. The terminal double bonds of both allenyl moieties served exclusively as the two π-components. In particular, this newly developed method was shown to be a powerful tool for the construction of bicyclo[6.3.0]undecadienones, which have hardly been prepared by the known Pauson-Khand (-type) reac-tions. The bicyclo[7.3.0]dodecadienone homologue (one extra carbon) could be formed in rather low yields. Alternatively, novel cycloisomerizations of bis(phenylsulfonylallene) derivatives with catalysis by the same Rh~1 complex under N_2 readily produced the 3,4-dimethylene-2,5-bis(phenylsulfonyl)cyclononene and the corresponding cyclooctene and cycloheptene frameworks.
机译：新型[{RhCl（CO）dppp} _2]在CO催化下双（苯基磺酰基烯丙基）衍生物的分子内羰基化[2 + 2 + 1]环加成反应，导致双（苯基磺酰基）双环[n.3.0]骨架的容易形成（n = 4-6），已经开发。两个烯基部分的末端双键仅充当两个π-组分。特别是，这种新开发的方法显示出是构建双环[6.3.0]十一碳二烯酮的有力工具，而已知的Pauson-Khand（-型）反应很难制备这种双环[6.3.0]十一碳二烯。双环[7.3.0] dodecadienone的同系物（多出一个碳）可以很低的产率形成。或者，在相同的Rh-1配合物在N_2的催化下，双（苯磺酰基烯丙基）衍生物的新型环异构化反应容易产生3,4-二亚甲基-2,5-双（苯磺酰基）环壬烯以及相应的环辛烯和环庚烯骨架。

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