A Novel NaI-Promoted Ring Expansion of Cyclopropylidene Alcohols to Dihydropyrans

Weijun Fu; Xian Huang; Ying Lin

doi:10.1055/s-2007-968016

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Synlett 2007(2): 0321-0323
DOI: 10.1055/s-2007-968016

LETTER

A Novel NaI-Promoted Ring Expansion of Cyclopropylidene Alcohols to Dihydropyrans

Weijun Fu^a, Xian Huang*^a,b, Ying Lin^a
^a Department of Chemistry, Zhejiang University (Xixi Campus), Hangzhou 310028, P. R. of China
Fax: +86(571)88807077; e-Mail: huangx@mail.hz.zj.cn;
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

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Publication History

Received 15 October 2006
Publication Date:
24 January 2007 (online)

Abstract
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Abstract

A novel and efficient approach to prepare dihydropyrans via the ring expansion of cyclopropylidene alcohols in the presence of NaI in AcOH-MeCN was reported. The key feature in the transformation is the effect of the iodide anion.

Key words

dihydropyrans - ring expansion - cyclopropylidene alcohols - iodide anion

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16

Typical Procedure for the Synthesis of Compound 3.
A solution of 1a (160 mg, 1.0 mmol) with NaI (225 mg, 1.5 mmol) in 5 mL of MeCN-AcOH (10:1) was stirred at 80 °C for 12 h. The mixture was then diluted with 10 mL of H₂O and extracted three times with Et₂O. The organic phases were combined and dried over MgSO₄. After evaporation, the residues were purified via chromatography on silica gel with n-hexane-EtOAc as the eluent to afford 108 mg (67%) of 3a as a liquid. IR (neat): 1652, 1600, 1448 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.25-7.34 (m, 5 H), 6.19-6.21 (m, 1 H), 4.50 (q, J = 2.8 Hz, 2 H), 3.85 (t, J = 5.6 Hz, 2 H), 2.30-2.34 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 138.4, 136.1, 128.5, 127.3, 124.7, 121.2, 66.8, 64.0, 25.5. MS (70 eV): m/z (%) = 160 (36.26) [M⁺].