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Enantioselective, High‐Yielding Synthesis of Alcohol‐Functionalized Diphosphanes Utilizing Asymmetric Control with a Chiral Auxiliary
Author(s) -
Pullarkat Sumod A.,
Cheow Yuen Lin,
Li Yongxin,
Leung PakHing
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900095
Subject(s) - chemistry , stereocenter , enantioselective synthesis , alcohol , stereoselectivity , yield (engineering) , enantiomer , naphthalene , organic chemistry , medicinal chemistry , catalysis , stereochemistry , materials science , metallurgy
Enantiomerically pure, alcohol‐functionalized diphosphane ligands carrying one phosphorus and three carbon stereogenic centers were generated from the Diels–Alder reactions of phosphane‐functionalized terminal alkenols [3‐(diphenylphosphanyl)but‐3‐en‐1‐ol and 2‐(diphenylphosphanyl)prop‐2‐en‐1‐ol] with 3,4‐dimethyl‐1‐phenyl‐1 H ‐phosphole. The reactions were promoted and controlled by the organoplatinum complex containing ortho ‐metalated ( R )‐[1‐(dimethylamino)ethyl]naphthalene, and both cycloadditions showed excellent regio‐ and stereoselectivity under mild conditions with only one enantiomer being formed. The products were isolated in high yield and were characterized by single‐crystal X‐ray diffraction analysis. Their structures in solution were analyzed by 2D 1 H– 1 H ROESY NMR spectroscopy. Subsequent decomplexation and repreparation of the products proved the optical purity of the alcohol‐functionalized, chiral diphosphanes formed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)