Ligand dependence of molybdenum-catalyzed alkylations. Molybdenum-isonitrile complexes as a new class of highly reactive alkylation catalysts
- Univ. of Wisconsin, Madison (United States); Stanford Univ., CA (United States)
A series of molybdenum complexes bearing {alpha}-diimine, N,N{prime}-diarylideneethylenediamine, and isonitrile ligands have been prepared and evaluated for their ability to catalyze alkylations by using allyl acetates and especially allyl sulfones. (bpy)Mo(CH{sub 3}CN)(CO){sub 3} proved to be a very effective catalyst in contrast to bpyMO(CO){sub 4}. The addition of isonitrile ligands to molybdenum hexacarbonyl generates the most effective molybdenum catalysts known to date. The reactive catalyst proved to be Mo(RNC){sub 4}(CO){sub 2}. With this new catalyst, a much broader range of substrates can be employed including many that failed or reacted very poorly by using molybdenum hexacarbonyl. The regioselectivity also differs from that obtained with molybdenum hexacarbonyl. The stereochemistry of the reaction proceeds with very clean net retention of configuration even under conditions that produced diastereomeric mixtures with molybdenum hexacarbonyl. A mechanistic rationale that accounts for the seemingly disparate complexes that are catalysts is presented.
- OSTI ID:
- 5757588
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 112:26; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACETATES
ALKANES
ALKENES
ALKYLATION
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACID SALTS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
COMPLEXES
CYCLOALKANES
ELEMENTS
HOMOGENEOUS CATALYSIS
HYDROCARBONS
ISONITRILES
KETONES
LIGANDS
MAGNETIC RESONANCE
METALS
MOLYBDENUM
MOLYBDENUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RESONANCE
SULFONES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS