Rapid-Injection NMR Study of Iodo- and Cyano-Gilman Reagents with 2-Cyclohexenone: Observation of π-Complexes and Their Rates of Formation
- 29 October 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (46) , 13650-13651
- https://doi.org/10.1021/ja027744s
Abstract
Rapid-injection is a very useful technique for the preparation of temperature-sensitive and air-sensitive compounds in the cold, nitrogen-filled probe of an NMR spectrometer. We have used this method to prepare solutions of π-complexes from 2-cyclohexenone and prototypical cuprates Me2CuLi·LiI and Me2CuLi·LiCN, and we have assigned structures on the basis of 1H and 13C NMR. In each case two π-complexes were observed, and in the former, their rates of formation were measured by rapid-injection 1H NMR and EXSY spectroscopy. These results provide insights into the normal and anomalous conjugate addition reactions of organocuprates.Keywords
This publication has 17 references indexed in Scilit:
- The Use of15N NMR Spectroscopy To Resolve the “Higher Order Cyanocuprate” Controversy:15N,6Li, and13C NMR Spectroscopic Investigations of CuCN-Derived Butyl CupratesAngewandte Chemie International Edition in English, 1998
- New Copper Chemistry. 23. Preparation of Ethereal Lithium Dimethylcuprates (Me2CuLi)2 and Me2CuLi.cntdot.LiI Displaying Narrow Line Width 13C NMR ResonancesOrganometallics, 1995
- New insight into the structure of organocuprate .pi.-complexes by determination of 13C,13C coupling constantsJournal of the American Chemical Society, 1994
- New copper chemistry. 21. Phenylcopper(I) and diphenylcuprate(I): characterization of aggregation states by carbon-13 NMR spectroscopyJournal of the American Chemical Society, 1993
- New copper chemistry. 17. Higher-order cyanocuprates: are they real?Journal of the American Chemical Society, 1990
- New copper chemistry. 16. Mechanism of organocuprate conjugate addition: observation of cuprate-olefin complexes and lithium-coordinated intermediates in the reaction of lithium dimethylcuprate(I) with 10-methyl-.DELTA.1,9-2-octaloneJournal of the American Chemical Society, 1989
- Direct Michael Additions of Silyl Groups to α,β‐Unsaturated β‐Arylketones and an α‐Benzylidenelactone with Mixtures Obtained from Copper(I) Cyanide, Butyllithium and ChlorosilanesAngewandte Chemie International Edition in English, 1988
- The Gilman reagent Ph2CuLi and higher-order Ph3CuLi2: carbon-13 and lithium-6 NMR in dimethyl sulfideJournal of the American Chemical Society, 1988
- Kinetics and mechanism of self-protonation reactions in organic electrochemical processesJournal of the American Chemical Society, 1985
- High-field rapid injection NMR: observation of unstable primary ozonide intermediatesThe Journal of Organic Chemistry, 1984