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Synthesis 2005(19): 3389-3397  
DOI: 10.1055/s-2005-918465
PAPER
© Georg Thieme Verlag Stuttgart · New York

Using a Temporary Silicon Connection in a Highly Stereoselective Synthesis of a New Class of Cyclic Allenylsilanes

Rui Ramalhoa, Julien Beigneta,, Alexander C. Humphriesb, Liam R. Cox*a
a School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
Fax: +44(121)4144403; e-Mail: l.r.cox@bham.ac.uk;
b The Neuroscience Research Centre, Merck, Sharp & Dohme, Terlings Park, Harlow, Essex, CM20 2QR, UK
Further Information

Publication History

Received 9 September 2005
Publication Date:
14 November 2005 (online)

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Abstract

Aldehyde 4 reacts in the presence of TMSOTf and an acid scavenger to provide the corresponding oxasilacycle 5 in very good yield and as a single diastereoisomer. The sense of 1,3-ste­reoinduction serves to introduce a 1,3-syn-diol relationship into the cyclic product. This is in accord with a previous study involving an analogous intramolecular allylation.

Key words

cyclisations - intramolecular allenylation - Lewis acids - stereoselective synthesis - Temporary Silicon Connection

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1

Current address: Metcalf Center for Science and Engineering, Boston University, 590, Commonwealth Avenue, Boston, MA 02215-2521, USA.

4

Tri-tert-butylpyrimidine (TTBP) and 2,6-di-tert-butyl-4-methylpyridine (2,6-DTBMP) were equally effective in this role.

11

The silyl tether is part of a vinylsilane in this intermediate and will be less effective in stabilising the β-vinyl carbocation on geometric grounds.

15

Propargyltrimethylsilane is commercially available although expensive and invariably contaminated with varying amounts of allenyltrimethylsilane. We find it more convenient to prepare the reagent ourselves.