Rh(I)-catalyzed Pauson-Khand reaction and cycloisomerization of allenynes: selective preparation of monocyclic, bicyclo[m.3.0], and bicyclo[5.2.0] ring systems.
Rh(I)-catalyzed Pauson-Khand reaction and cycloisomerization of allenynes: selective preparation of monocyclic, bicyclo[m.3.0], and bicyclo[5.2.0] ring systems.
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DOI：
10.1021/jo050770z
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发表时间：
2005-08
期刊：
影响因子：
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通讯作者：
C. Mukai;F. Inagaki;T. Yoshida;Katsuya Yoshitani;Yasuyuki Hara;S. Kitagaki
中科院分区：
文献类型：
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作者：
C. Mukai;F. Inagaki;T. Yoshida;Katsuya Yoshitani;Yasuyuki Hara;S. Kitagaki
[反应：见正文]Rh(I)催化的烯丙炔的PKR被发现适用于构建氮杂双环[5.3.0]十二烯酮和恶二环[5.3.0]十二烯酮骨架。此外，在CO摩尔比为10atm的条件下，建立了一种可靠的方法来构建10-单取代双环[5.3.0]十碳-1，7-二烯-9-酮环体系。在氮气气氛下，4-苯磺酰基-2，3-二烯-8-氮杂环己烯在Rh(I)催化下的环异构化反应得到了相应的环己烯衍生物，而氯代烯丙炔则根据烯丙基末端的取代方式生成环庚烯衍生物和/或双环[5.2.0]骨架。因此，选择合适的起始烯丙炔和反应条件，可以选择性地合成2-phenylsulfonylbicyclo[5.3.0]deca-1，7-dien-9-ones(Pauson-Khand型产物)、3-alkylidene-1-phenylsulfonyl-2-vinylcycloheptene衍生物和双环[5.2.0]壬烯骨架。
[reaction: see text] Rhodium(I)-catalyzed PKR of allenynes was found to be applicable for constructing azabicyclo[5.3.0]decadienone as well as oxabicyclo[5.3.0]decadienone frameworks. In addition, a reliable procedure for constructing a 10-monosubstituted bicyclo[5.3.0]deca-1,7-dien-9-one ring system by the rhodium(I)-catalyzed PKR of allenynes was developed under the condition of 10 atm of CO. Investigation of the rhodium(I)-catalyzed cycloisomerization of 4-phenylsulfonylnona-2,3-dien-8-ynes under nitrogen atmosphere gave the corresponding cyclohexene derivatives, whereas the C1-homologated allenynes produced cycloheptene derivatives and/or bicyclo[5.2.0]nonene skeletons depending on the substitution pattern at the allenic terminus. Thus, proper choice of the starting allenynes and reaction conditions led to the selective formation of 2-phenylsulfonylbicyclo[5.3.0]deca-1,7-dien-9-ones (Pauson-Khand-type product), 3-alkylidene-1-phenylsulfonyl-2-vinylcycloheptene derivatives, and bicyclo[5.2.0]nonene frameworks.