Synthetic Studies towards Cembranoids via the Heck Reaction

Hajime Yokoyama; Tomonori Satoh; Takaya Furuhata; Masahiro Miyazawa; Yoshiro Hirai

doi:10.1055/s-2006-950438

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Synlett 2006(16): 2649-2651
DOI: 10.1055/s-2006-950438

LETTER

Synthetic Studies towards Cembranoids via the Heck Reaction

Hajime Yokoyama, Tomonori Satoh, Takaya Furuhata, Masahiro Miyazawa, Yoshiro Hirai*
University of Toyama, Department of Chemistry, Gofuku 3190, Toyama 930-8555, Japan
e-Mail: hirai@sci.u-toyama.ac.jp;

Further Information

Publication History

Received 28 June 2006
Publication Date:
22 September 2006 (online)

Abstract
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Abstract

The Heck reaction was employed for the construction of the macrocyclic cembranoid skeleton.

Key words

palladium - Heck reaction - ring closure - macrocycles - cembranoids

References and Notes

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5

The ketone 3 was synthesized in 15 steps from geraniol according to usual methods.

6

Data for 10: IR (neat): 1716 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.21 (d, 1 H, J = 15.6 Hz), 6.15 (d, 1 H, J = 15.6 Hz), 5.72 (s, 1 H), 5.02-4.98 (m, 2 H), 4.17 (q, 2 H, J = 7.2 Hz), 2.92-2.74 (m, 2 H), 2.35-1.81 (m, 10 H), 1.61 (s, 3 H), 1.57 (s, 3 H), 1.31-1.29 (m, 6 H), 0.92 (s, 9 H), 0.10 (s, 3 H), 0.08 (s, 3 H); an NOE of 4.3% was observed between H₁ and H₂ (Figure [3] ). EIMS: m/z = 446 (M⁺).

9

Data for 12: IR (neat): 1722 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.60 (d, 1 H, J = 16.4 Hz), 6.19 (d, 1 H, J = 16.4 Hz), 5.65 (s, 1 H), 5.18-5.05 (m, 1 H), 5.04-4.95 (m, 1 H), 4.17 (q, 2 H, J = 7.2 Hz), 2.82-2.65 (m, 2 H), 2.51-1.75 (m, 8 H), 1.56 (s, 6 H), 1.61 -1.48 (m, 2 H), 1.35-1.19 (m, 6 H), 0.95-0.80 (m, 9 H), 0.08-0.04 (m, 3 H). EIMS: m/z = 389 [M⁺ - t-Bu].