First Long-Distance S(RN)1 on a propargylic chloride

Manon Roche (1, 2) , Thierry Terme (2) , Patrice Vanelle (2)

1 APHM - Assistance Publique - Hôpitaux de Marseille
2 ICR - Institut de Chimie Radicalaire

We report here the first example of a Long-Distance S(RN)1 (LD-S(RN)1) reaction on a propargylic chloride. The reaction of 1-(3-chloroprop-1-ynyl)-4-nitrobenzene (1) with nitronate anions led to both the formation of the C-alkylation product through an LD-S(RN)1 mechanism and the ethylenic compound resulting from nitrous acid elimination on the C-alkylation product 2. In contrast with previous work on LD-S(RN)1 reactivity, no O-alkylation product was observed. Only one original product 4 was isolated under phase transfer conditions, resulting from a nucleophilic attack by 2-nitropropane anion on the electrophilic allcyne. This LD-S(RN)1 reactivity did not extend to sulfinate anions: the reaction of 1 with sulfinate anions yielded original ethylenic disulfone compounds which were formed via an ionic process. (C) 2012 Elsevier Ltd. All rights reserved.

Domaines: Chimie

Manon Roche, Thierry Terme, Patrice Vanelle. First Long-Distance S(RN)1 on a propargylic chloride. Tetrahedron Letters, 2012, 53 (32), pp.4184--4187. ⟨10.1016/j.tetlet.2012.05.150⟩. ⟨hal-01460417⟩