Structure-selectivity relationship in the cleavage of spirocyclopropyl oxindoles: An experimental and theoretical investigation

J. Benjamín García-Vázquez; Angel E. Bañuelos-Hernández; Joel J. Trujillo-Serrato; Oscar R. Suárez-Castillo; Armando Ariza-Castolo; Martha S. Morales-Ríos

doi:10.1016/j.molstruc.2017.05.099

Structure-selectivity relationship in the cleavage of spirocyclopropyl oxindoles: An experimental and theoretical investigation

J. Benjamín García-Vázquez, Angel E. Bañuelos-Hernández, Joel J. Trujillo-Serrato, Oscar R. Suárez-Castillo, Armando Ariza-Castolo, Martha S. Morales-Ríos

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

Abstract

Heterogeneous catalytic hydrogenation of strained nitrile substituted spirocyclopropyl oxindoles in acetic anhydride, allowed to the regioselective formation of ring-opened 2-oxohomotryptamines accompanied by the ring-retained spirocyclopropyl acetamides as by products. The C3[sbnd]C9 bond fission would be induced by H atom attack via the plausible intermediacy of a stabilized benzolactam carbon-centered radical. The substituent effects on the stability of such radicals were analyzed in terms of the energy of SOMO orbitals, showing good agreement with σ_m Hammett constants. The theoretical results reflect experimental findings on the reactivity of the analyzed compounds.

Original language	English
Pages (from-to)	184-191
Number of pages	8
Journal	Journal of Molecular Structure
Volume	1145
DOIs	https://doi.org/10.1016/j.molstruc.2017.05.099
State	Published - 5 Oct 2017
Externally published	Yes

Keywords

Hammett analysis
Hydrogenation
SOMO orbital
Spirocyclopropyl oxindoles

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10.1016/j.molstruc.2017.05.099

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García-Vázquez, J. B., Bañuelos-Hernández, A. E., Trujillo-Serrato, J. J., Suárez-Castillo, O. R., Ariza-Castolo, A., & Morales-Ríos, M. S. (2017). Structure-selectivity relationship in the cleavage of spirocyclopropyl oxindoles: An experimental and theoretical investigation. Journal of Molecular Structure, 1145, 184-191. https://doi.org/10.1016/j.molstruc.2017.05.099

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title = "Structure-selectivity relationship in the cleavage of spirocyclopropyl oxindoles: An experimental and theoretical investigation",

abstract = "Heterogeneous catalytic hydrogenation of strained nitrile substituted spirocyclopropyl oxindoles in acetic anhydride, allowed to the regioselective formation of ring-opened 2-oxohomotryptamines accompanied by the ring-retained spirocyclopropyl acetamides as by products. The C3[sbnd]C9 bond fission would be induced by H atom attack via the plausible intermediacy of a stabilized benzolactam carbon-centered radical. The substituent effects on the stability of such radicals were analyzed in terms of the energy of SOMO orbitals, showing good agreement with σm Hammett constants. The theoretical results reflect experimental findings on the reactivity of the analyzed compounds.",

keywords = "Hammett analysis, Hydrogenation, SOMO orbital, Spirocyclopropyl oxindoles",

author = "Garc{\'i}a-V{\'a}zquez, {J. Benjam{\'i}n} and Ba{\~n}uelos-Hern{\'a}ndez, {Angel E.} and Trujillo-Serrato, {Joel J.} and Su{\'a}rez-Castillo, {Oscar R.} and Armando Ariza-Castolo and Morales-R{\'i}os, {Martha S.}",

note = "Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",

year = "2017",

month = oct,

day = "5",

doi = "10.1016/j.molstruc.2017.05.099",

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

volume = "1145",

pages = "184--191",

journal = "Journal of Molecular Structure",

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TY - JOUR

T1 - Structure-selectivity relationship in the cleavage of spirocyclopropyl oxindoles

T2 - An experimental and theoretical investigation

AU - García-Vázquez, J. Benjamín

AU - Bañuelos-Hernández, Angel E.

AU - Trujillo-Serrato, Joel J.

AU - Suárez-Castillo, Oscar R.

AU - Ariza-Castolo, Armando

AU - Morales-Ríos, Martha S.

PY - 2017/10/5

Y1 - 2017/10/5

N2 - Heterogeneous catalytic hydrogenation of strained nitrile substituted spirocyclopropyl oxindoles in acetic anhydride, allowed to the regioselective formation of ring-opened 2-oxohomotryptamines accompanied by the ring-retained spirocyclopropyl acetamides as by products. The C3[sbnd]C9 bond fission would be induced by H atom attack via the plausible intermediacy of a stabilized benzolactam carbon-centered radical. The substituent effects on the stability of such radicals were analyzed in terms of the energy of SOMO orbitals, showing good agreement with σm Hammett constants. The theoretical results reflect experimental findings on the reactivity of the analyzed compounds.

AB - Heterogeneous catalytic hydrogenation of strained nitrile substituted spirocyclopropyl oxindoles in acetic anhydride, allowed to the regioselective formation of ring-opened 2-oxohomotryptamines accompanied by the ring-retained spirocyclopropyl acetamides as by products. The C3[sbnd]C9 bond fission would be induced by H atom attack via the plausible intermediacy of a stabilized benzolactam carbon-centered radical. The substituent effects on the stability of such radicals were analyzed in terms of the energy of SOMO orbitals, showing good agreement with σm Hammett constants. The theoretical results reflect experimental findings on the reactivity of the analyzed compounds.

KW - Hammett analysis

KW - Hydrogenation

KW - SOMO orbital

KW - Spirocyclopropyl oxindoles

UR - http://www.scopus.com/inward/record.url?scp=85019882316&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2017.05.099

DO - 10.1016/j.molstruc.2017.05.099

M3 - Artículo

SN - 0022-2860

VL - 1145

SP - 184

EP - 191

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

ER -

Structure-selectivity relationship in the cleavage of spirocyclopropyl oxindoles: An experimental and theoretical investigation

Abstract

Keywords

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