Diastereoselective Synthesis of Seven- and Eight-Membered Oxabicycles via Prins-Type Cyclization

Hyun Jung Kang; Sang Hee Kim; Ae Nim Pae; Hun Yeong Koh; Moon Ho Chang; Kyung il Choi; So-Yeop Han; Yong Seo Cho

doi:10.1055/s-2004-832841

LETTER

Diastereoselective Synthesis of Seven- and Eight-Membered Oxabicycles via Prins-Type Cyclization

Hyun Jung Kang^a, Sang Hee Kim^a, Ae Nim Pae^a, Hun Yeong Koh^a, Moon Ho Chang^a, Kyung il Choi^a, So-Yeop Han^b, Yong Seo Cho*^a
^a Biochemicals Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650, Korea
Fax: +82(2)9585189; e-Mail: ys4049@kist.re.kr;
^b Division of Molecular Life Sciences, Ewha Womans University, 1-1 Daehyun-dong, Seodaemun-gu, Seoul, 120-750, Korea

Abstract

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Abstract

A novel methodology for the diastereoselective synthesis of seven- and eight-membered oxabicycles bearing dimethylidene via Prins-type cyclization was developed. The reaction takes place in the presence of TMSOTf in diethyl ether at -78 °C.

Key words

diastereoselective synthesis - seven- and eight-membered oxabicycles - Prins reaction

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References

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4

A General Procedure for Preparation of Seven- and Eight-Membered Oxabicycles:
To a stirred solution of allenol substrates 1 (or 2) (0.36 mmol) in dry Et₂O (3.0 mL) was added TMSOTf (0.36 mmol) at -78 °C. The mixture was allowed to warm to r.t. slowly for 3 h, then stirred at r.t. for 0.5-1 h until completion of the reaction. The reaction mixture was diluted with 10 mL of Et₂O, and then H₂O (4mL) was added. The organic solution was washed with brine, and the organic layer was dried (MgSO₄), filtered, and concentrated. Purification by flash column chromatography provided the desired cycloadducts. Compound 5a: ¹H NMR (300 MHz, CDCl₃): δ = 5.00 (s, 1 H), 5.29 (s, 1 H), 4.78 (t, 2 H, J = 5.6 Hz), 4.53 (br s, 1 H), 2.69 (br d, 1 H, J = 12.1 Hz), 2.00-2.36 (m, 2 H), 1.64-1.85 (m, 3 H), 1.51 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 152.51, 143.41, 112.19, 104.33, 81.86, 76.23, 42.42, 37.47, 30.22, 22.87 ppm. IR (KBr): 2926, 1731, 1458 cm^-1. GC-MS: m/z = 150 [M⁺]. HRMS: m/z calcd for C₁₀H₁₄O: 150.1045; found: 150.1043. Compound 6a: ¹H NMR (300 MHz, CDCl₃): δ = 5.25 (s, 1 H), 5.13 (s, 1 H), 4.80 (s, 1 H), 4.74 (s, 1 H), 4.23 (br t, 1 H, J = 6.3 Hz), 2.00-1.25 (m, 8 H), 1.35 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 152.3, 146.1, 109.2, 107.6, 74.0, 69.2, 40.3, 38.6, 30.5, 29.1, 17.9 ppm. IR (KBr): 2924, 1730, 1454 cm^-1. GC-MS: m/z = 164 [M⁺]. HRMS: m/z calcd for C₁₁H₁₆O: 164.1200; found: 164.1201.

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