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3.4.7.6.2 Variation 2: Conjugate Addition Reactions

DOI: 10.1055/sos-SD-003-00274

Heaney, H.; Christie, S.Science of Synthesis, (20043625.

One of the most comprehensively studied areas of copper chemistry is 1,4-addition to α,β-unsaturated systems. The fact that this area of chemistry was reviewed 30 years ago gives an indication of the volume of work that has been carried out.[‌131‌,‌201‌] In this respect, dialkylcuprates are among the most widely used reagents since they are reactive, relatively easy to prepare, and, perhaps most importantly, give reproducible results. As with other copper reagents, the source of the copper and the quality of all reagents is of critical importance, and one should always screen a number of different copper reagents in any new reaction. However, in the main, Gilman cuprates react well in conjugate addition reactions and have provided a wealth of mechanistic information over the years. One study that deserves mention is the effect that coordinating solvents have on conjugate addition reactions.[‌1644‌] The necessity of having an ethereal solvent is highlighted in this paper. If a Michael reaction was carried out in toluene, the product of 1,2-addition was isolated. When diethyl ether was used, at least 2 equivalents were required but a significant jump to almost exclusive 1,4-addition was noted. This suggests that theoretical calculations on the stabilization of a copper(III) intermediate during the conjugate process may be correct.

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