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The chemistry of small ring compounds. Part 46. Reduction of 1-halocyclopropyl sulfides by thiolates

✍ Scribed by R. Jorritsma; H. Steinberg; Th. J. de Boer

Publisher
Elsevier Science
Year
2010
Tongue
English
Weight
888 KB
Volume
101
Category
Article
ISSN
0165-0513

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✦ Synopsis

Abstract

The reaction of 1‐halocyclopropyl sulfides with sodium alkanethiolates in protic or aprotic solvents leads to high yields of cyclopropyl sulfides, in which halogen has been replaced by hydrogen. The complementary oxidized product is, in most cases, the thioketone or thioaldehyde derived from the alkanethiolate. The reduction is unaffected by radical scavengers or by oneelectron donors.

Reaction kinetics indicate that the reduction proceeds via the 1‐(alkylthio)cyclopropyl cation. A mechanism is discussed (Scheme 9) in which this ambident cation is attacked by thiolate on sulfur. In the intermediary sulfonium ylid an intramolecular hydrogen shift leads to the observed products.

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## Abstract 1‐Hydroxy‐ and 1‐halocyclopropyl sulfides can be conveniently prepared starting from cyclopropanone. Cyclopropyl sulfides with halogen or a dimethylsulfonium group in the α‐position can be transformed into 1‐substituted cyclopropyl sulfides with a variety of nucleophiles. This means tha

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Previously we described the efficient oxidation of l-methoxycyclopropanol 1 with Cu\*+ Ions to methyl acrylate 2 and dimethyl adipate 3 via the methyl P-propionate radical 2. It was proved by labelling experiments 131 that the \*