Rapid-injection NMR study of iodo- and cyano-Gilman reagents with 2-cyclohexenone: observation of pi-complexes and their rates of formation

Steven H Bertz; Clifford M Carlin; Daniel A Deadwyler; Michael D Murphy; Craig A Ogle; Paul H Seagle

doi:10.1021/ja027744s

Rapid-injection NMR study of iodo- and cyano-Gilman reagents with 2-cyclohexenone: observation of pi-complexes and their rates of formation

J Am Chem Soc. 2002 Nov 20;124(46):13650-1. doi: 10.1021/ja027744s.

Authors

Steven H Bertz¹, Clifford M Carlin, Daniel A Deadwyler, Michael D Murphy, Craig A Ogle, Paul H Seagle

Affiliation

¹ Department of Chemistry, University of North Carolina-Charlotte, UNCC Station, Charlotte, North Carolina 28223, USA. cogle@email.uncc.edu

PMID: 12431075
DOI: 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 pi-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 pi-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.