Mechanism of triflimide-catalyzed [3,3]-sigmatropic rearrangements of N-allylhydrazones-predictions and experimental validation

被引：16

作者：

Gutierrez, Osvaldo ^{[2
]}

Strick, Benjamin F. ^{[1
]}

Thomson, Regan J. ^{[1
]}

Tantillo, Dean J. ^{[2
]}

机构：

[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

CHEMICAL SCIENCE | 2013年 / 4卷 / 10期

基金：

美国国家科学基金会;

关键词：

3,3 SIGMATROPIC REARRANGEMENT; COPE REARRANGEMENTS; BOND FORMATION; 1,5-HEXADIENE;

D O I：

10.1039/c3sc51564h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Computational analysis of the triflimide catalyzed [3,3]-sigmatropic rearrangement of N-allylhydrazones, using density functional theory calculations, is reported. Key mechanistic insight was obtained and predictions derived therefrom were confirmed experimentally through temperature dependence studies. The computational results have led to the development of electron deficient N-allylhydrazones capable of reacting under mild reaction conditions. Application of the rearrangement to form a new sp(3) stereogenic center is reported for the first time.

引用

页码：3997 / 4003

页数：7

共 32 条

[21] Stereocontrolled Synthesis of Contiguous C(sp3)-C(aryl) Bonds by Lanthanide(III)-Catalyzed Domino Aryl-Claisen [3,3]-Sigmatropic Rearrangements
Ramadhar, Timothy R.
Kawakami, Jun-ichi
Lough, Alan J.
Batey, Robert A.
ORGANIC LETTERS, 2010, 12 (20) : 4446 - 4449
[22] MERCURY(II)-CATALYZED 3,3-SIGMATROPIC REARRANGEMENTS OF ALLYLIC N,N-DIMETHYLCARBAMATES - MILD METHOD FOR ALLYLIC EQUILIBRATIONS AND CONTRA-THERMODYNAMIC ALLYLIC ISOMER ENRICHMENTS
OVERMAN, LE
CAMPBELL, CB
JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (20): : 3338 - 3340
[23] Gold-Catalyzed Addition of N-Hydroxy Heterocycles to Alkynes and Subsequent 3,3-Sigmatropic Rearrangement
Kumar, Manish
Scobie, Martin
Mashuta, Mark S.
Hammond, Gerald B.
Xu, Bo
ORGANIC LETTERS, 2013, 15 (04) : 724 - 727
[24] Rapid and Effective Reaction of 2-Methylpyridin-N-oxides with Triphosgene via a [3,3]-Sigmatropic Rearrangement: Mechanism and Applications
Li, Hao
Xia, Hong-Cheng
Nie, Fang-Yuan
Song, Qin-Hua
JOURNAL OF ORGANIC CHEMISTRY, 2021, 86 (12): : 8308 - 8318
[25] Palladium-catalyzed [3,3] sigmatropic rearrangement of (allyloxy)iminodiazaphospholidines: Allylic transposition of C-O and C-N functionality
Lee, EE
Batey, RA
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (14) : 1865 - 1868
[26] CYCLOADDUCTS OF C-NITROSOCARBONYL COMPOUNDS AND ERGOSTERYL ACETATE - [3,3]SIGMATROPIC REARRANGEMENTS OF N-AROYL-3,6-DIHYDRO-1,2-OXAZINES
KIRBY, GW
MACKINNON, JWM
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1985, (04): : 887 - 892
[27] Acid-Catalyzed [3,3] Sigmatropic Rearrangement of N-Cbz-Diaryl Hydrazide for the Synthesis of Mono-N-Cbz-1,1′-biaryl-2,2′-diamine
Suh, Sung-Eun
Park, In-Keol
Lim, Byeong-Yun
Cho, Cheon-Gyu
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (03) : 455 - 457
[28] Annulated N-Heterocycles by Tandem Gold(I)-Catalyzed [3,3]-Rearrangement/Nazarov Reaction of Propargylic Ester Derivatives: an Experimental and Computational Study
Petrovic, Martina
Scarpi, Dina
Fiser, Bela
Gomez-Bengoa, Enrique
Occhiato, Ernesto G.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2015, 2015 (18) : 3943 - 3956
[29] DECARBOXYLATIVE 1-AZA-1'-OXA[3,3]SIGMATROPIC REARRANGEMENTS OF ENOLIZABLE OR ENOLIZED N-ARYL-N,O-DIACYLHYDROXYLAMINES TO ORTHO-(N-ACYLAMINO)ARYL KETONES, ESTERS, AND AMIDES - NEW SYNTHETIC METHOD FOR ORTHO ALKYLATION
COATES, RM
SAID, IM
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (07) : 2355 - 2357
[30] Metabolic regio- and stereoselectivity of cytochrome P450 2D6 towards 3,4-methylenedioxy-N-alkylamphetamines:: in silico predictions and experimental validation
Keizers, PHJ
de Graaf, C
de Kanter, FJJ
Oostenbrink, C
Feenstra, KA
Commandeur, JNM
Vermeulen, NPE
JOURNAL OF MEDICINAL CHEMISTRY, 2005, 48 (19) : 6117 - 6127

← 1 2 3 4 →