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HERO ID
8332459
Reference Type
Journal Article
Title
(Nitroaryl)sulfinyl-Substituted Allenes. Novel and Convenient Propargyl Alcohol Synthons in 4 + 2 Cycloaddition Chemistry
Author(s)
Padwa, A; Bullock, WH; Norman, BH; Perumattam, J
Year
1991
Is Peer Reviewed?
Yes
Journal
Journal of Organic Chemistry
ISSN:
0022-3263
EISSN:
1520-6904
Volume
56
Issue
13
Page Numbers
4252-4259
Language
English
DOI
10.1021/jo00013a033
Abstract
(Nitroaryl)sulfmyl-substituted allenes are conveniently prepared by treating propargyl alcohol or methyl 3-hydroxy-2-butynoate with a (nitroaryl)sulfenyl chloride and triethylamine. These activated allenes undergo 4 + 2 cycloaddition across the C1C2 Ï-bond. The initially formed allylic sulfoxide readily undergoes a 2,3-sigmatropic rearrangement to produce a stable sulfenate ester that is easily cleaved with thiophilic reagents. The dienophilic reactivity of the (nitroaryl)sulfinyl-substituted allene is much greater than the corresponding propargyl alcohol, and the cycloaddition also proceeds with high regioselectivity. The Diels-Alder reaction of [(2-nitrophenyl)-sulfinyl]propadiene with Danishefskyâs diene affords meta-substituted benzyl alcohols in high yield. Reaction of the more highly activated methyl 2-[(2-nitrophenyl)sulfinyl]-2,3-butadienoate with Danisheskyâs diene followed by treatment of the resulting sulfenate ester with triethyl phosphite produces substituted phthalides in excellent yield. The (2,4-dinitrophenyl)sulfinyl-substituted allene was found to react smoothly with a variety of nitrones to give sulfenate esters of isoxazolidines. These allenyl sulfoxides correspond to formal equivalents of propargyl alcohol, which itself is too unreactive to undergo Diels-Alder chemistry or 1,3-dipolar cycloaddition with nitrones or nitrile oxides. © 1991, American Chemical Society. All rights reserved.
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