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Synlett 2007(6): 0986-0988  
DOI: 10.1055/s-2007-973859
LETTER
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Catalysis of Intramolecular Morita-Baylis-Hillman and Related Reactions by Chiral Rhenium-Containing Phosphines of the Formula (η5-C5H5)Re(NO)(PPh3)(CH2PAr2)

Florian Seidel, John A. Gladysz*
Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Henkestraße 42, 91054 Erlangen, Germany
e-Mail: John.Gladysz@chemie.uni-erlangen.de;
Further Information

Publication History

Received 7 December 2006
Publication Date:
26 March 2007 (online)

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Abstract

The racemic rhenium-containing phosphine (η5-C5H5)Re(NO)(PPh3)(CH2PPh2) catalyzes intramolecular Morita-Baylis-Hillman reactions of four R(CO)CH=CH(CH2) n CH2CHO species (n = 1 or 2; R = Ph, S-i-Pr, p-Tol, Me) in benzene or chlorobenzene at 20 °C. The products R(CO)CH=CH(CH2) n CH2CHOH are isolated in 88-99% yields and 38-74% ee when enantiopure S-configured catalyst is used. Similar reactions of R(CO)CH=CHCH2CH2CH=CH(CO)R (R = Ph, S-i-Pr) give R(CO)C=CHCH2CH2CHCH2(CO)R in 63-87% yields and 42-56% ee.

Key words

Morita-Baylis-Hillman - Rauhut-Currier - phosphine - enantioselective catalysis - organocatalysis - cyclization

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    Enantiopure catalysts: The preceding reactions were repeated on 0.0010-0.0020 g scales. The products were analyzed by HPLC using Chiralcel OD, Chiralpak AD-H or Chiralpak AS-H columns.

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14

All products were characterized by NMR (1H, 13C) and IR spectroscopy, and these data are available from the authors upon request; 3a,d and 5a have been reported previously.11a,15,16
Typical data (3b): 1H NMR (400 MHz, CDCl3): δ = 1.39 [d, (CH 3)2CH, 3 J(H,H) = 7.2 Hz, 6 H], 1.82-1.91 (m, C=CHCHH′, 1 H), 2.27-2.46 (2 m, C=CHCHH′, CHH′CHOH, 2 H) 2.62-2.73 (m, CHH′CHOH, 1 H), 2.78 (br s, CHOH, 1 H), 3.74 [sep, 3 J(H,H) = 7.2 Hz, (CH3)2CH, 1 H], 5.13-5.16 (m, CHOH, 1 H), 6.89 [dd, 3 J(H,H) = 2.8, 2.8 Hz, C=CHCHH′, 1 H] ppm. 13C{1H} NMR (101 MHz, CDCl3): δ = 23.0 [s, ( C H3)2CH], 30.9 (s, C=CHCH2), 31.8 (s, CH2CHOH), 34.3 [s, (CH3)2 CH], 75.7 (s, CHOH), 144.4 [s, (CO)C=CH], 145.2 [s, (CO)C=CH], 190.1 [s, (CO)C=CH] ppm. IR (thin film): 1613 (s, νC=C), 1648 (s, νCO), 3450 (br, νOH) cm-1.