On the Synthesis and Addition Reactions of Chiral N-Heterocyclic Diphosphines

Reaction of chiral N-heterocyclic chlorophosphines with lithium diphenylphosphide or of achiral N-heterocyclic chlorophosphines with optically active lithium menthyl phosphide produces chiral N-heterocyclic diphosphines which can be utilized in subsequent diphosphination reactions with activated alk...

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Bibliographic Details
Published in:Zeitschrift für Naturforschung. B, A journal of chemical sciences Vol. 67; no. 8; pp. 765 - 773
Main Authors: Foerster, Daniela, Hartenbach, Ingo, Nieger, Martin, Gudat, Dietrich
Format: Journal Article
Language:English
Published: BERLIN Walter De Gruyter 01.08.2012
Subjects:
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
1ST RESOLUTION
PHOSPHORUS
PHOSPHINE
COMPLEXES
Diphosphines
HIGHLY ENANTIOSELECTIVE HYDROFORMYLATION
Chiral Ligands
N-Heterocyclic Phosphines
BIS(TRIARYL)PHOSPHINE
LIGANDS
Diphosphination
ALPHA-(ACYLAMINO)ACRYLIC ACIDS
2,2'-BIS(DIPHENYLPHOSPHINO)-1,1'-BINAPHTHYL BINAP
ASYMMETRIC HYDROGENATION
Phosphine Complexes
ISSN:0932-0776, 1865-7117
Online Access:Get more information
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Summary:Reaction of chiral N-heterocyclic chlorophosphines with lithium diphenylphosphide or of achiral N-heterocyclic chlorophosphines with optically active lithium menthyl phosphide produces chiral N-heterocyclic diphosphines which can be utilized in subsequent diphosphination reactions with activated alkenes or alkynes. The reaction with alkynes proceeds stereospecifically to produce Z-ethylene-1,2-bisphosphines which are readily converted to nickel(II) or palladium( 1) complexes. Reactions with alkenes are synthetically less useful as the addition proceeds without any chiral induction at the newly formed stereocenters to yield inseparable mixtures of diastereomeric products. The molecular structures of chiral Z-ethylene-1,2-bisphosphine complexes and of a chiral N-heterocyclic chlorophosphine have been determined by single-crystal X-ray diffraction.
ISSN:0932-0776
1865-7117
DOI:10.5560/ZNB.2012-0177