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Synlett 2002(6): 0931-0932
DOI: 10.1055/s-2002-31927
LETTER
© Georg Thieme Verlag Stuttgart · New York

Catalytic, Enantioselective Hetero-Diels-Alder Reaction with Novel, Chiral Bis-Titanium(IV) Catalyst

Satoshi Kii, Takuya Hashimoto, Keiji Maruoka*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
Fax: +81(75)7534041; e-Mail: maruoka@kuchem.kyoto-u.ac.jp;
Further Information

Publication History

Received 16 March 2002
Publication Date:
07 February 2007 (online)

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Abstract

Our recently designed chiral bis-titanium(IV) catalyst can be successfully utilized for the catalytic enantioselective hetero-Diels-Alder reaction of aldehyde and Danishefsky’s diene. The high asymmetric induction is achievable in the case of sterically less hindered aldehydes.

Key words

hetero-Diels-Alder - asymmetric synthesis - catalyst - titanium(IV) complex

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4

The hetero-Diels-Alder reaction of phenylpropargyl aldehyde 3 (R = C≡ CPh) proceeded smoothly with a chiral mono-Ti(IV) complex 2 (10 mol%) to give adduct 4 (R = C≡ CPh) in 47% yield. In contrast, however, the reactivity of the hetero-Diels-Alder reaction of benzaldehyde 3 (R = Ph) are lowered (e.g., 29% yield) under similar reaction condition with a chiral mono-Ti(IV) 2 (10 mol%).