Stereochemistry modulates the catalytic hydrogenolysis of nitrile-substituted cyclopropanes

Daphne E. González-Juárez; J. Benjamín García-Vázquez; Violeta Zúñiga-García; Joel J. Trujillo-Serrato; Oscar R. Suárez-Castillo; Pedro Joseph-Nathan; Martha S. Morales-Ríos

doi:10.1016/j.tet.2012.06.025

Stereochemistry modulates the catalytic hydrogenolysis of nitrile-substituted cyclopropanes

Daphne E. González-Juárez, J. Benjamín García-Vázquez, Violeta Zúñiga-García, Joel J. Trujillo-Serrato, Oscar R. Suárez-Castillo, Pedro Joseph-Nathan, Martha S. Morales-Ríos

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

11 Scopus citations

Abstract

The study of Raney-Ni catalyzed chemo- and regioselective hydrogenolysis of diastereomeric nitrile-substituted spirocyclopropyloxindoles is presented. The chemoselectivity outcome of the reaction is remarkably influenced by the relative stereochemistry of the nitrile-substituted spirocyclopropyloxindoles. Chemo- and high regioselective cyclopropane ring-opening occurs from the syn diastereomers to give the corresponding 3-propylacetamide derivatives. X-ray crystallographic studies together with DFT model chemistry calculations indicate that chemo- and regioselectivity are directly dependent on the bond length asymmetry of the cyclopropane ring.

Original language	English
Pages (from-to)	7187-7195
Number of pages	9
Journal	Tetrahedron
Volume	68
Issue number	35
DOIs	https://doi.org/10.1016/j.tet.2012.06.025
State	Published - 2 Sep 2012
Externally published	Yes

Keywords

Chemoselectivity
Cyclopropane
DFT study
Hydrogenolysis
Regioselectivity
Stereochemistry

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10.1016/j.tet.2012.06.025

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@article{4c391f32d5ea453a94c85295a91a948f,

title = "Stereochemistry modulates the catalytic hydrogenolysis of nitrile-substituted cyclopropanes",

abstract = "The study of Raney-Ni catalyzed chemo- and regioselective hydrogenolysis of diastereomeric nitrile-substituted spirocyclopropyloxindoles is presented. The chemoselectivity outcome of the reaction is remarkably influenced by the relative stereochemistry of the nitrile-substituted spirocyclopropyloxindoles. Chemo- and high regioselective cyclopropane ring-opening occurs from the syn diastereomers to give the corresponding 3-propylacetamide derivatives. X-ray crystallographic studies together with DFT model chemistry calculations indicate that chemo- and regioselectivity are directly dependent on the bond length asymmetry of the cyclopropane ring.",

keywords = "Chemoselectivity, Cyclopropane, DFT study, Hydrogenolysis, Regioselectivity, Stereochemistry",

author = "Gonz{\'a}lez-Ju{\'a}rez, {Daphne E.} and Garc{\'i}a-V{\'a}zquez, {J. Benjam{\'i}n} and Violeta Z{\'u}{\~n}iga-Garc{\'i}a and Trujillo-Serrato, {Joel J.} and Su{\'a}rez-Castillo, {Oscar R.} and Pedro Joseph-Nathan and Morales-R{\'i}os, {Martha S.}",

note = "Funding Information: Financial support by CONACYT grants 81810 and 139736 is gratefully acknowledged.",

year = "2012",

month = sep,

day = "2",

doi = "10.1016/j.tet.2012.06.025",

language = "Ingl{\'e}s",

volume = "68",

pages = "7187--7195",

journal = "Tetrahedron",

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number = "35",

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TY - JOUR

T1 - Stereochemistry modulates the catalytic hydrogenolysis of nitrile-substituted cyclopropanes

AU - González-Juárez, Daphne E.

AU - García-Vázquez, J. Benjamín

AU - Zúñiga-García, Violeta

AU - Trujillo-Serrato, Joel J.

AU - Suárez-Castillo, Oscar R.

AU - Joseph-Nathan, Pedro

AU - Morales-Ríos, Martha S.

N1 - Funding Information: Financial support by CONACYT grants 81810 and 139736 is gratefully acknowledged.

PY - 2012/9/2

Y1 - 2012/9/2

N2 - The study of Raney-Ni catalyzed chemo- and regioselective hydrogenolysis of diastereomeric nitrile-substituted spirocyclopropyloxindoles is presented. The chemoselectivity outcome of the reaction is remarkably influenced by the relative stereochemistry of the nitrile-substituted spirocyclopropyloxindoles. Chemo- and high regioselective cyclopropane ring-opening occurs from the syn diastereomers to give the corresponding 3-propylacetamide derivatives. X-ray crystallographic studies together with DFT model chemistry calculations indicate that chemo- and regioselectivity are directly dependent on the bond length asymmetry of the cyclopropane ring.

AB - The study of Raney-Ni catalyzed chemo- and regioselective hydrogenolysis of diastereomeric nitrile-substituted spirocyclopropyloxindoles is presented. The chemoselectivity outcome of the reaction is remarkably influenced by the relative stereochemistry of the nitrile-substituted spirocyclopropyloxindoles. Chemo- and high regioselective cyclopropane ring-opening occurs from the syn diastereomers to give the corresponding 3-propylacetamide derivatives. X-ray crystallographic studies together with DFT model chemistry calculations indicate that chemo- and regioselectivity are directly dependent on the bond length asymmetry of the cyclopropane ring.

KW - Chemoselectivity

KW - Cyclopropane

KW - DFT study

KW - Hydrogenolysis

KW - Regioselectivity

KW - Stereochemistry

UR - http://www.scopus.com/inward/record.url?scp=84863831700&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2012.06.025

DO - 10.1016/j.tet.2012.06.025

M3 - Artículo

SN - 0040-4020

VL - 68

SP - 7187

EP - 7195

JO - Tetrahedron

JF - Tetrahedron

IS - 35

ER -

Stereochemistry modulates the catalytic hydrogenolysis of nitrile-substituted cyclopropanes

Abstract

Keywords

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