title: Allylmagnesium Halides Do Not React Chemoselectively Because Reaction Rates Approach the Diffusion Limit.
abstract: Competition experiments demonstrate that additions of allylmagnesium halides to carbonyl compounds, unlike additions of other organomagnesium reagents, occur at rates approaching the diffusion rate limit. Whereas alkylmagnesium and alkyllithium reagents could differentiate between electronically or sterically different carbonyl compounds, allylmagnesium reagents reacted with most carbonyl compounds at similar rates. Even additions to esters occurred at rates competitive with additions to aldehydes. Only in the case of particularly sterically hindered substrates, such as those bearing tertiary alkyl groups, were additions slower.
authors.affiliation: Department of Chemistry, New York University , 100 Washington Square East, New York, New York 10003, United States.
authors.forename: Jacquelyne A
authors.initials: JA
authors.lastname: Read
authors.affiliation: Department of Chemistry, New York University , 100 Washington Square East, New York, New York 10003, United States.
authors.forename: K A
authors.identifier: 0000-0002-8515-0301
authors.initials: KA
authors.lastname: Woerpel
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D000498:Allyl Compounds / Q000737:chemistry*; D004058:Diffusion; D006846:Hydrocarbons, Halogenated / Q000737:chemistry*; D008274:Magnesium / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000447:Aldehydes; D000498:Allyl Compounds; D006846:Hydrocarbons, Halogenated; D009942:Organometallic Compounds; D008274:Magnesium