Use of Chiral Sulfoxide in the Asymmetric Synthesis of (+)-Virol C

Hélio A.  Stefani; Paulo H.  Menezes; Iguatemi M.  Costa; Diogo O.  Silva; Nicola  Petragnani

doi:10.1055/s-2002-32973

LETTER

Use of Chiral Sulfoxide in the Asymmetric Synthesis of (+)-Virol C

Hélio A. Stefani*^a, Paulo H. Menezes^b, Iguatemi M. Costa^a, Diogo O. Silva^a, Nicola Petragnani^c
^a Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo, SP, Brazil
Fax: +55(11)38154418; e-Mail: hstefani@usp.br;
^b Depto. de Química Fundamental, Universidade Federal de Pernambuco, Recife, PE, Brazil
^c Instituto de Química, Universidade de São Paulo, São Paulo, SP, Brazil

Abstract

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Abstract

The total synthesis of virol C 1 was accomplished using a diastereoselective carbonyl reduction induced by a chiral sulfoxide, a Pummerer rearrangement to give the corresponding aldehyde fragment, and coupling reactions using Wittig and Cadiot-Chodkiewicz protocols.

Key words

natural products - chiral sulfoxides - total synthesis - copper-coupling - Pummerer reaction

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References

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Compound 7. [α]_D +192º, (c 0.97, CHCl₃). ¹H NMR (CDCl₃) δ: 7.52 (d, J = 8 Hz, 2 H, Ho); 7.35 (d, J = 8 Hz, 2 H, Hm); 4.20-4.12 (m, 1 H, CHOH); 3.02 (dd, J ₁ = 13.5 Hz, J ₂ = 10 Hz, 1 H); 2.67 (dd, J ₁ = 3.5 Hz, J ₂ = 10 Hz, 1 H); 2.42 (s, 3 H); 1.82 (br. 1 H, OH); 1.73-1.24 (m, 12 H), 0.86 (t, J = 6.5 Hz, 3 H).¹³C NMR (CDCl₃) δ:141.53 (1 C, p); 139.58 (1 C, ipso);130.07 (2 C, m); 124.01 (2 C, o); 66.64 (1 C, CHOH); 61.50; 37.04; 31.75; 29.34; 29.15; 25.14; 22.61; 21.40; 14.07. IR (KBr) 3367; 2954; 2921; 2852; 1087; 1005; 812 cm^-1. MS m/z (%): 282 (M⁺, 2.10), 265(30); 140(100); 92(32); 69(17); 55(15); 43(18). Calcd for C₁₆H₂₆O₂S; C, 68.04; H, 9.28. Found: C, 68.12; H, 9.20. Compound 1. [α]_D +6.2, (c = 0.80, MeOH) (lit.⁴ [α]_D +6.4, (c = 0.82, MeOH).¹H NMR (CDCl₃) δ: 6.27 (dd, J ₁ = 16 Hz, J ₂ = 6 Hz, 1 H); 5.73 (d, J = 16 Hz, 1 H); 4.15 (br, 1 H); 3.74 (t, J ₁ = 6 Hz, 2 H); 2.47 (t, J = 6 Hz, 2 H); 1.80 (quint, J = 6 Hz, 2 H); 1.52-1.48 (m, 2 H); 1.47-1.26 (m, 10 H); 0.88 (t, J = 6 Hz, 3 H). ¹³C NMR (CDCl₃) δ: 149.0; 108.6; 83.5; 74.7; 73.3; 72.1; 65.5; 61.4; 36.9; 31.7; 30.8; 29.3; 29.1; 25.1; 22.5; 16.0; 13.9. IR (CHCl₃): 3608, 3439, 3013, 2932, 2859, 2236, 2140 cm^-1. MS m/z (%): 262 (M⁺) 231; 217; 191; 177; 163; 149; 135; 127; 57. Calcd for C₁₇H₂₆O₂; C, 77.81; H, 9.99. Found: C, 77.41; H, 10.10.