Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

Solymar Negretti; Carolyn M. Cohen; Jane J. Chang; David M. Guptill; Huw M.L. Davies

doi:10.1016/j.tet.2015.05.045

Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

Solymar Negretti, Carolyn M. Cohen, Jane J. Chang, David M. Guptill, Huw M.L. Davies

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

Abstract

Abstract Highly functionalized cyclopropanecarboxylates were readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichloroethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the nature of the ester group and the chiral dirhodium tetracarboxylate catalyst. The prolinate catalyst Rh₂(S-DOSP)₄ was the optimum catalyst for asymmetric intermolecular cyclopropanation of TMSE diazoesters with styrene, while Rh₂(R-BPCP)₄ was the optimum catalyst for TCE diazoesters.

Original language	English (US)
Article number	26763
Pages (from-to)	7415-7420
Number of pages	6
Journal	Tetrahedron
Volume	71
Issue number	39
DOIs	https://doi.org/10.1016/j.tet.2015.05.045
State	Published - Aug 17 2015

Bibliographical note

Funding Information:
Changming Qin is acknowledged for preliminary data on the synthesis of 8 from the methyl ester 7 and the observation that the hydrolysis of the methyl ester in 7 results in racemization of the product. This work was supported by the National Science Foundation under the CCI Center for Selective C–H Functionalization , CHE-1205646 , the National Institutes of Health ( GM099142 ) and unrestricted support from Novartis.

Publisher Copyright:
© 2015 Elsevier Ltd.

Keywords

Asymmetric cyclopropanation
Cyclopropanes
Dirhodium catalysis
Donor/acceptor carbenoids

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10.1016/j.tet.2015.05.045

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title = "Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates",

abstract = "Abstract Highly functionalized cyclopropanecarboxylates were readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichloroethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the nature of the ester group and the chiral dirhodium tetracarboxylate catalyst. The prolinate catalyst Rh2(S-DOSP)4 was the optimum catalyst for asymmetric intermolecular cyclopropanation of TMSE diazoesters with styrene, while Rh2(R-BPCP)4 was the optimum catalyst for TCE diazoesters.",

keywords = "Asymmetric cyclopropanation, Cyclopropanes, Dirhodium catalysis, Donor/acceptor carbenoids",

author = "Solymar Negretti and Cohen, {Carolyn M.} and Chang, {Jane J.} and Guptill, {David M.} and Davies, {Huw M.L.}",

note = "Funding Information: Changming Qin is acknowledged for preliminary data on the synthesis of 8 from the methyl ester 7 and the observation that the hydrolysis of the methyl ester in 7 results in racemization of the product. This work was supported by the National Science Foundation under the CCI Center for Selective C–H Functionalization , CHE-1205646 , the National Institutes of Health ( GM099142 ) and unrestricted support from Novartis. Publisher Copyright: {\textcopyright} 2015 Elsevier Ltd.",

year = "2015",

month = aug,

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doi = "10.1016/j.tet.2015.05.045",

language = "English (US)",

volume = "71",

pages = "7415--7420",

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T1 - Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

AU - Negretti, Solymar

AU - Cohen, Carolyn M.

AU - Chang, Jane J.

AU - Guptill, David M.

AU - Davies, Huw M.L.

N1 - Funding Information: Changming Qin is acknowledged for preliminary data on the synthesis of 8 from the methyl ester 7 and the observation that the hydrolysis of the methyl ester in 7 results in racemization of the product. This work was supported by the National Science Foundation under the CCI Center for Selective C–H Functionalization , CHE-1205646 , the National Institutes of Health ( GM099142 ) and unrestricted support from Novartis. Publisher Copyright: © 2015 Elsevier Ltd.

PY - 2015/8/17

Y1 - 2015/8/17

N2 - Abstract Highly functionalized cyclopropanecarboxylates were readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichloroethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the nature of the ester group and the chiral dirhodium tetracarboxylate catalyst. The prolinate catalyst Rh2(S-DOSP)4 was the optimum catalyst for asymmetric intermolecular cyclopropanation of TMSE diazoesters with styrene, while Rh2(R-BPCP)4 was the optimum catalyst for TCE diazoesters.

AB - Abstract Highly functionalized cyclopropanecarboxylates were readily prepared by rhodium-catalyzed cyclopropanation of alkenes with aryldiazoacetates and styryldiazoaceates, in which the ester functionality is either trimethylsilylethyl (TMSE) or trichloroethyl (TCE). By having labile protecting groups on the ester, chiral triarylcyclopropane carboxylate ligands were conveniently prepared. The asymmetric induction during cyclopropanation is dependent on the nature of the ester group and the chiral dirhodium tetracarboxylate catalyst. The prolinate catalyst Rh2(S-DOSP)4 was the optimum catalyst for asymmetric intermolecular cyclopropanation of TMSE diazoesters with styrene, while Rh2(R-BPCP)4 was the optimum catalyst for TCE diazoesters.

KW - Asymmetric cyclopropanation

KW - Cyclopropanes

KW - Dirhodium catalysis

KW - Donor/acceptor carbenoids

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Enantioselective dirhodium(II)-catalyzed cyclopropanations with trimethylsilylethyl and trichloroethyl aryldiazoacetates

Abstract

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