Rhodium(I)-Catalyzed Intramolecular Carbonylative [2+2+1] Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
Rhodium(I)-Catalyzed Intramolecular Carbonylative [2+2+1] Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
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DOI：
10.1002/chem.200903568
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Mukai, Chisato
中科院分区：
文献类型：
--
作者：
Kawamura, Takamasa;Inagaki, Fuyuhiko;Mukai, Chisato
新型[{RhCl(CO)dppp}(2)]催化双(苯磺酰基联烯)衍生物在CO下发生分子内羰基化[2+2+1]环加成反应，从而容易形成双(苯磺酰基)双环[n.3.0]骨架(n=4-6)。两个丙二烯基部分的末端双键专门充当两个π-组分。特别是，这种新开发的方法被证明是构建双环[6.3.0]十一碳烯酮的有力工具，而已知的 Pauson Khand（-型）反应几乎无法制备双环[6.3.0]十一碳烯酮。双环[7.3.0]十二碳二烯酮同系物（一个额外的碳）可以以相当低的产率形成。或者，在N-2下通过相同的Rh-I络合物催化双(苯磺酰基联烯)衍生物的新型环异构化很容易产生3,4-二亚甲基-2,5-双(苯磺酰基)环壬烯和相应的环辛烯和环庚烯骨架。
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 pi-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) reactions. 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-I complex under N-2 readily produced the 3,4-dimethylene-2,5-bis(phenylsulfonyl)cyclononene and the corresponding cyclooctene and cycloheptene frameworks.