定义Definition
根岸偶联是钯或镍催化下，有机锌试剂与有机卤化物或三氟甲磺酸酯偶联形成 C–C 键的反应，可连接 sp³、sp²、sp 碳。
The Negishi coupling joins an organozinc reagent with an organic halide or triflate under palladium or nickel catalysis to form a C–C bond, linking sp³, sp² and sp carbons.
特点Features
有机锌试剂活性高于硼、锡试剂，转金属化快，常在室温进行；同时比格氏试剂、有机锂温和，能容忍酯、腈、酮等官能团。对烷基–烷基偶联也较有效。缺点是有机锌对水和空气敏感。
Organozincs are more reactive than boron or tin reagents and transmetalate fast, often at room temperature, yet are milder than Grignard or organolithium reagents and tolerate esters, nitriles and ketones. They also handle alkyl–alkyl couplings. They are, however, moisture- and air-sensitive.
由来Origin
根岸英一于 1977 年报道。他因此与赫克、铃木章共获 2010 年诺贝尔化学奖。
Reported by Ei-ichi Negishi in 1977; he shared the 2010 Nobel Prize in Chemistry with Heck and Suzuki.
试剂制备Reagent preparation
有机锌可由锌粉直接插入卤代烃（诺赫尔的 LiCl 活化法）、或由有机锂/格氏试剂与 ZnCl₂ 转金属化得到。
Organozincs are made by direct zinc insertion into halides (Knochel’s LiCl activation) or by transmetalation of organolithium/Grignard reagents with ZnCl₂.
反应Reactions
Pd(PPh₃)₄ 或 Pd/膦配体、Ni(acac)₂，THF，0 °C 至室温
Pd(PPh₃)₄ or Pd/phosphine, or Ni(acac)₂, in THF at 0 °C to room temperature
氧化加成。
Oxidative addition.
有机锌转金属化。
Transmetalation from zinc.
还原消除。
Reductive elimination.
酯基不受影响。
The ester survives.
年表Timeline
- 1977
根岸报道钯/镍催化有机锌偶联
Negishi reports Pd/Ni-catalysed organozinc coupling
- 2010
根岸共获诺贝尔化学奖
Negishi shares the Nobel Prize in Chemistry