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Enantioselectivity and cis/trans-Selectivity in Dirhodium(II)-Catalyzed addition of diazoacetates to olefins

✍ Scribed by Paul Müller; Corine Baud; Doïna Ené; Sharokh Motallebi; Michael P. Doyle; Bridget D. Brandes; Alexey B. Dyatkin; Marjorie M. See

Publisher
John Wiley and Sons
Year
1995
Tongue
German
Weight
741 KB
Volume
78
Category
Article
ISSN
0018-019X

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✦ Synopsis

The Rh"-catalyzed carbenoid addition of diazoacetates to olefins was investigated with [Rh2{(4S)-phox},] (1; phox = tetrakis[(4S)-tetrahydro-4-phenyloxazol-2-one]), [Rh2{(2S)-mepy},] (2; mepy = tetrakis[methyl (2s)tetrahydro-5-oxopyrrole-2-carboxylate]), and [Rh,(OAc),] (3). While catalysis with 2 and 3 afford preferentially rrcms-cyclopropanecarboxylates, the cis-isomers are the major products with 1. In general, the enantioselectivities achieved with 1 and 2 are comparable. Additions catalyzed by 1 are strongly sensitive to steric effects. Highly substituted olefins afford cyclopropanes in only poor yield. The preferential cis-selectivity observed in reactions catalyzed by 1 is attributed to dominant interactions between the ligand of the catalyst and the substituents of both olefin and diazoacetate, which overrule the steric interactions between olefin and diazoacetate in the transition state for carbene transfer.

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We thank MIUR, Rome (FIRB funds), "Progetto Stereoselezione in Chimica Organica -Metodologie ed Applicazioni", and the University of Bologna (funds for selected research topics) for financial support of this research.

Kinetic Resolution of Epoxides by a CC B
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✍ Marco Bandini; Pier Giorgio Cozzi; Paolo Melchiorre; Achille Umani-Ronchi 📂 Article 📅 2004 🏛 John Wiley and Sons 🌐 English ⚖ 133 KB 👁 2 views

We thank MIUR, Rome (FIRB funds), "Progetto Stereoselezione in Chimica Organica -Metodologie ed Applicazioni", and the University of Bologna (funds for selected research topics) for financial support of this research.