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

被引：0

作者：

Garcia-Vazquez, J. Benjamin ^{[1
,2
]}

Banuelos-Hernandez, Angel E. ^{[1
]}

Trujillo-Serrato, Joel J. ^{[1
]}

Suarez-Castillo, Oscar R. ^{[3
]}

Ariza-Castolo, Armando ^{[1
]}

Morales-Rios, Martha S. ^{[1
,2
]}

机构：

[1] Inst Politecn Nacl, Dept Quim, Ctr Invest & Estudios Avanzados, Apartado 14-740, Mexico City 07000, DF, Mexico

[2] Inst Politecn Nacl, Programa Posgrado Farmacol, Ctr Invest & Estudios Avanzados, Apartado 14-740, Mexico City 07000, DF, Mexico

[3] Univ Autonoma Estado Hidalgo, Area Acad Quim, Mineral De La Reforma 42184, Hidalgo, Mexico

来源：

JOURNAL OF MOLECULAR STRUCTURE | 2017年 / 1145卷

关键词：

Spirocyclopropyl oxindoles; Hydrogenation; SOMO orbital; Hammett analysis; CARBON-CARBON BOND; CATALYTIC HYDROGENOLYSIS; MODEL CHEMISTRY; CYCLOPROPANE; HYDROGENATION; RESONANCE; REARRANGEMENT; ENERGETICS; STABILITY; CONSTANTS;

D O I：

10.1016/j.molstruc.2017.05.099

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 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 am Hammett constants. The theoretical results reflect experimental findings on the reactivity of the analyzed compounds. (C) 2017 Elsevier B.V. All rights reserved.

引用

页码：184 / 191

页数：8

共 40 条

[1] 1H NMR Spectra. Part 28: Proton chemical shifts and couplings in three-membered rings. A ring current model for cyclopropane and a novel dihedral angle dependence for 3JHH couplings involving the epoxy proton [J].

Abraham, Raymond J. ;

Leonard, Paul ;

Tormena, Claudio F. .

MAGNETIC RESONANCE IN CHEMISTRY, 2012, 50 (04) :305-313

[2]

Augustine R.L., 1965, CAALYTIC HYDROGENATI

[3] A proposed modification of CBS-4M model chemistry for application to molecules of increasing molecular size [J].

Benassi, R .

THEORETICAL CHEMISTRY ACCOUNTS, 2001, 106 (04) :259-263

[4] CATALYTIC HYDROGENOLYSIS OF CYCLOPROPANES - METAL INSERTION INTO A SATURATED CARBON-CARBON BOND AS THE KEY STEP [J].

BESSARD, Y ;

SCHLOSSER, M .

TETRAHEDRON, 1991, 47 (07) :1231-1238

[5] Ring Current Model and Anisotropic Magnetic Response of Cyclopropane [J].

Carion, Raphael ;

Champagne, Benoit ;

Monaco, Guglielmo ;

Zanasi, Riccardo ;

Pelloni, Stefano ;

Lazzeretti, Paolo .

JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2010, 6 (07) :2002-2018

[6] Radical aryl migration reactions and synthetic applications [J].

Chen, Zhi-Min ;

Zhang, Xiao-Ming ;

Tu, Yong-Qiang .

CHEMICAL SOCIETY REVIEWS, 2015, 44 (15) :5220-5245

[7] METHYLENECYCLOPROPANE REARRANGEMENT AS A PROBE FOR FREE-RADICAL SUBSTITUENT EFFECTS - SIGMA.-VALUES FOR COMMONLY ENCOUNTERED CONJUGATING AND ORGANOMETALLIC GROUPS [J].

CREARY, X ;

MEHRSHEIKHMOHAMMADI, ME ;

MCDONALD, S .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (15) :3254-3263

[8] The heterogeneous catalytic hydrogenation of cumulated allene-cyclopropanes:: 1-(2′-methylpropenylidene)-2-phenylcyclopropane [J].

Crombie, L ;

Fernando, CEC .

JOURNAL OF CHEMICAL RESEARCH-S, 1998, (07) :366-+

[9] Theoretical study of X-H bond energetics (X = C, N, O, S): Application to substituent effects, gas phase acidities, and redox potentials [J].

DiLabio, GA ;

Pratt, DA ;

LoFaro, AD ;

Wright, JS .

JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (11) :1653-1661

[10] SUBSTITUENT EFFECTS ON BENZYL RADICAL ELECTRON-SPIN-RESONANCE HYPERFINE COUPLING-CONSTANTS - THE SIGMA-ALPHA.SCALE BASED UPON SPIN DELOCALIZATION [J].

DUST, JM ;

ARNOLD, DR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (05) :1221-1227

← 1 2 3 4 →