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Tetrakis[(4 S )‐4‐phenyloxazolidin‐2‐one]dirhodium(II) and Its Catalytic Applications for Metal Carbene Transformations
Author(s) -
Doyle Michael P.,
Winchester William R.,
Protopopova Mari.,
Müller Paul,
Bernardinelli Gérald,
Ene Doina,
Motallebi Sharokh
Publication year - 1993
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19930760606
Subject(s) - cyclopropane , chemistry , intramolecular force , carbene , cyclopropene , intermolecular force , catalysis , stereochemistry , carboxylate , metal , selectivity , medicinal chemistry , molecule , organic chemistry , ring (chemistry)
The synthesis and X‐ray structure of the binuclear complex tetrakis[(4 S )‐4‐phenyloxazolidin‐2‐one]‐dirhodium(II) ([Rh 2 {(4 S )‐phox} 4 ]) are reported. Structure‐selectivity comparisons are made for typical metal carbene transformations, such as inter‐ and intramolecular cyclopropane formation, intermolecular cyclopropene formation and intramolecular C–H insertions of diazoacetates and diazoacetamides. The enantioselectivity achieved in the [Rh 2 {(4 S )‐phox} 4 ]‐catalyzed reactions is intermediate between that of [Rh 2 {(5 S )‐mepy} 4 ] and [Rh 2 {(4 R )‐bnox} 4 ], which were described previously (mepy = methyl 5‐oxopyrrolidine‐2‐carboxylate; bnox = 4‐benzyloxazolidin‐2‐one). In contrast to other catalyzed intermolecular cyclopropane formations, those using [Rh 2 {(4 S )‐phox} 4 ] result preferentially in formation of the cis ‐cyclopropane.