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Synlett 2010(8): 1235-1238  
DOI: 10.1055/s-0029-1219815
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Intramolecular [2+2+2] Cycloaddition of Dienynes for the Construction of Adjacent Three Chiral Centers

Takanori Shibata*, Mayumi Otomo, Kohei Endo
Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Okubo, Shinjuku, Tokyo 169-8555, Japan
Fax: +81(3)52868098; e-Mail: tshibata@waseda.jp;
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Publication History

Received 13 February 2010
Publication Date:
09 April 2010 (online)

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Abstract

A chiral rhodium catalyst realized the first intramolecular [2+2+2] cycloaddition of yne-ene-enes, and chiral multicyclic cyclohexenes with adjacent three chiral centers were afforded with high to excellent ee.

Key words

catalysis - chirality - cycloaddition - rhodium - multi­cyclic

    Reference and Notes

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14

The counter anion of the Rh catalyst did not affect the yield of 2a and its ee (BF4: 74%, 87% ee, OTf: 69%, 86% ee).

15

The ene-type products and their isomerized products were also formed in each entry.

16

The reaction of carbon-tethered dienyne 1f did not proceeded even at 80 ˚C. Oxygen-tethered dienyne 1g was promptly consumed at r.t. but ene-type products were formed and no cycloadduct could be detected.

17

Based on Scheme  [²] , the absolute configuration of the tricyclic product would be determined at the formation of the bicyclic metallacyclopentene, which is the same interme-diate as that of [2+2+2] cycloaddition of enediynes, see ref. 7a.