An enantioconvergent halogenophilic nucleophilic substitution (S N 2X) reaction

Bimolecular nucleophilic substitution (S 2) plays a central role in organic chemistry. In the conventionally accepted mechanism, the nucleophile displaces a carbon-bound leaving group X, often a halogen, by attacking the carbon face opposite the C-X bond. A less common variant, the halogenophilic S...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2019-01, Vol.363 (6425), p.400-404
Main Authors: Zhang, Xin, Ren, Jingyun, Tan, Siu Min, Tan, Davin, Lee, Richmond, Tan, Choon-Hong
Format: Article
Language:English
Subjects:
Activated carbon
Azides (organic)
Bromides
Bromine
Carbon
Catalysis
Chemical bonds
Computer applications
Intermediates
Nitrogen
Nucleophiles
Organic chemistry
Steric hindrance
Substitution reactions
Sulfur
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Summary:Bimolecular nucleophilic substitution (S 2) plays a central role in organic chemistry. In the conventionally accepted mechanism, the nucleophile displaces a carbon-bound leaving group X, often a halogen, by attacking the carbon face opposite the C-X bond. A less common variant, the halogenophilic S 2X reaction, involves initial nucleophilic attack of the X group from the front and as such is less sensitive to backside steric hindrance. Herein, we report an enantioconvergent substitution reaction of activated tertiary bromides by thiocarboxylates or azides that, on the basis of experimental and computational mechanistic studies, appears to proceed via the unusual S 2X pathway. The proposed electrophilic intermediates, benzoylsulfenyl bromide and bromine azide, were independently synthesized and shown to be effective.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.aau7797