ReactNMR and ReactIR as Reaction Monitoring and Mechanistic Elucidation Tools: The NCS Mediated Cascade Reaction of α-Thioamides to α-Thio-β-chloroacrylamides

被引：70

作者：

Foley, David A. ^{[1
]}

Doecke, Christopher W. ^{[1
]}

Buser, Jonas Y. ^{[1
]}

Merritt, Jeremy M. ^{[2
]}

Murphy, Linda ^{[3
]}

Kissane, Marie ^{[3
]}

Collins, Stuart G. ^{[3
]}

Maguire, Anita R. ^{[3
,4
]}

Kaerner, Andreas ^{[1
]}

机构：

[1] Eli Lilly & Co, Lilly Corp Ctr, Analyt Sci Res & Dev, Indianapolis, IN 46285 USA

[2] Eli Lilly & Co, Lilly Corp Ctr, Chem Prod Res & Dev, Indianapolis, IN 46285 USA

[3] Univ Coll Cork, Analyt & Biol Chem Res Facil, Dept Chem, Cork, Ireland

[4] Univ Coll Cork, Analyt & Biol Chem Res Facil, Sch Pharm, Cork, Ireland

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 76卷 / 23期

关键词：

ONLINE NMR-SPECTROSCOPY; FLOW NMR; IN-SITU; 2,4,6-TRINITROANISOLE; TRANSFORMATION; KINETICS; STEP;

D O I：

10.1021/jo201212p

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

On-flow ReactIR and H-1 NMR reaction monitoring, coupled with in situ intermediate characterization, was used to aid in the mechanistic elucidation of the N-chlorosuccinirnide mediated transformation of an alpha-athioarnide. Multiple intermediates in this reaction cascade are identified and characterized, and in particular, spectroscopic evidence for the intermediacy of the chlorosulfonium ion in the chlorination of alpha-thioamides is provided. Further to this, solvent effects on the outcome of the transformation are discussed. This work also demonstrates the utility of using a combination of ReactIR and flow NMR reaction monitoring (ReactNMR) for characterizing complex multicomponent reaction mixtures.

引用

页码：9630 / 9640

页数：11

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