Desulfurization with nickel and cobalt boride: Scope, selectivity, stereochemistry, and deuterium-labeling studies
Journal Article
·
· Journal of Organic Chemistry; (United States)
- Univ. of Calgary, Alberta (Canada)
A variety of organosulfur compounds containing alkylthio and arylthio groups underwent reductive desulfurization under notably mild conditions when treated with nickel boride, generated in situ from nickel chloride hexahydrate and sodium borohydride in methanol-THF (3:1). Phenyl, chloro, and ester groups are not reduced under these conditions, while iodo, bromo, nitrile, aldehyde, ketone, cyclopropane, and olefinic functions are reduced either completely or partially. Deuterium-labeling studies indicate that the hydrogen that is incorporated into the product originates from both the sodium borohydride and the protic solvent, suggesting the intermediacy of dihydrogen. The epimers 3[alpha]- and 3[beta]-(phenylthio)cholestane afforded 3[alpha]- and 3[beta]-deuteriocholestane, respectively, demonstrating that the reaction proceeds with retention of configuration. The method may thus be employed for the stereospecific preparation of deuterated products from organosulfur compounds. Arguments are presented in support of a tentative mechanism involving an oxidative addition-reductive elimination sequence via a nickel hydride intermediate. 44 refs., 2 tabs.
- OSTI ID:
- 5999366
- Journal Information:
- Journal of Organic Chemistry; (United States), Journal Name: Journal of Organic Chemistry; (United States) Vol. 58:9; ISSN 0022-3263; ISSN JOCEAH
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
01 COAL, LIGNITE, AND PEAT
010402 -- Coal
Lignite
& Peat-- Purification & Upgrading
02 PETROLEUM
020400 -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BORIDES
BORON COMPOUNDS
CHEMICAL REACTIONS
COBALT BORIDES
COBALT COMPOUNDS
DESULFURIZATION
DEUTERIUM COMPOUNDS
HYDROGEN COMPOUNDS
KETONES
LABELLED COMPOUNDS
NICKEL BORIDES
NICKEL COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
REDUCTION
STEREOCHEMISTRY
TRANSITION ELEMENT COMPOUNDS
010402 -- Coal
Lignite
& Peat-- Purification & Upgrading
02 PETROLEUM
020400 -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BORIDES
BORON COMPOUNDS
CHEMICAL REACTIONS
COBALT BORIDES
COBALT COMPOUNDS
DESULFURIZATION
DEUTERIUM COMPOUNDS
HYDROGEN COMPOUNDS
KETONES
LABELLED COMPOUNDS
NICKEL BORIDES
NICKEL COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
REDUCTION
STEREOCHEMISTRY
TRANSITION ELEMENT COMPOUNDS