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Synthesis 2011(12): 1865-1879  
DOI: 10.1055/s-0030-1260602
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Isothiourea-Catalyzed Asymmetric O- to C-Carboxyl Transfer of Furanyl Carbonates

Caroline Joannesse, Louis C. Morrill, Craig D. Campbell, Alexandra M. Z. Slawin, Andrew D. Smith*
EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST, UK
Fax: +44(1334)463806; e-Mail: ads10@st-andrews.ac.uk;
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Publication History

Received 28 April 2011
Publication Date:
25 May 2011 (online)

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Abstract

The ability of a chiral isothiourea to promote the regio- and enantioselective O- to C-carboxyl transfer of a series of 3-alkyl-5-aryl- and 5-methyl-3-phenylfuranyl carbonates is examined, generating preferentially the α-regioisomers (α/γ up to 83:17) with high asymmetric induction (up to 83% ee).

Key words

isothiourea - organocatalysis - carboxyl transfer - furanyl carbonates - butenolides

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11

2 was readily prepared on a multigram scale by alkylation of the dianion of phenylacetic acid with 2-methyloxirane; see experimental section for synthesis.

15

(R)-TADMAP was kindly donated by Prof. Edwin Vedejs. Consistent with the literature, rearrangement of furanyl carbonate 5 with (R)-TADMAP gave a 60:40 mixture of α/γ regioisomers, with purification giving the major α-regio-isomer 8 in 49% yield and 85% ee.