Gilman-Type versus Lipshutz-Type Reagents: Competition in Lithiocuprate Chemistry

Gilman-Type versus Lipshutz-Type Reagents: Competition in Lithiocuprate Chemistry
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DOI:
10.1021/om801101u
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发表时间:
2009-01-12
期刊:
影响因子:
2.8
通讯作者:
Raithby, Paul R.
Raithby, Paul R.
中科院分区:
化学2区
文献类型:
--
作者:
Haywood, Joanna;Morey, James V.;Raithby, Paul R.

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CuCN与RLi和TMPLi(TMP = 2,2,6,6-四甲基哌啶)反应,得到Gilman型铜酸盐R(TMP)CuLi·nL(R = Ph,n = 3,L = THF 2; R = Me,n = 1,L = TMEDA 3). 3和3.LiCN已经在定向邻位铜化中进行了测试,数据表明Lipshutz型3.LiCN的效率提高; Lipshutz型和Gilman型制剂之间的竞争通过DFT方法合理化。
CuCN reacts with RLi and TMPLi (TMP = 2,2.6,6-tetramethylpiperidide) to give Gilman-type cuprates R(TMP)CuLi.nL (R = Ph, n = 3, L = THF 2; R = Me, n = 1, L = TMEDA 3). 3 and 3.LiCN have been tested in directed ortho cupration with data suggesting enhanced efficiency for Lipshutz-type 3.LiCN; competition between Lipshutz- and Gilman-type formulations is rationalized by DFT methods.