Cuprates, lithium, higher order, reaction with

Thienyl(cyano)copper lithium S Cu(CN)Li xhe reagent is obtained by reaction of thiophene with BuLi in THF at - 78° and then with CuCN at - 40°. The reagent is fairly stable and can be stored in THF at - 20° for about 2 months. It is inert, but is readily converted by addition of RLi or RMgX into a higher-order mixed cuprate, which is as efficient as the freshly prepared cuprate."1... 

A 1,2-metalate rearrangement of a higher order cuprate, known as a Kodenski rearrangement [64], was used as a key step in the synthesis of the marine antiinflammatory sesterterpenoid manoalide 95 (Scheme 9.20) [65]. Treatment of the alkenyl lithium 89 (prepared from the alkenylstannane 88 with s-BuLi in a diethyl ether-pentane mixture) with the homocuprate 91 (produced from iodoalkane 90) gave the iodoalkene 94 in 72% overall yield from 88. The reaction proceeds as fol-... 

Cuprate, dibutyl-, lithium, reaction with acetylene, 66, 62 Cuprates, higher order, 66, 57... 

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