定义Definition
赫克反应是钯催化下，芳基或乙烯基卤化物（或三氟甲磺酸酯）与烯烃在碱存在下偶联，生成取代烯烃的反应，产物通常为反式（E）构型。
The Heck reaction is the palladium-catalysed coupling of an aryl or vinyl halide (or triflate) with an alkene in the presence of base, giving a substituted alkene, usually with E geometry.
催化循环Catalytic cycle
Pd(0) 氧化加成 Ar–X；烯烃配位并顺式迁移插入 Ar–Pd 键（芳基加到位阻小的碳上）；绕 C–C 键旋转后发生顺式 β-氢消除，释放取代烯烃并生成 H–Pd–X；碱除去 HX 再生 Pd(0)。
Pd(0) oxidatively adds Ar–X; the alkene coordinates and inserts syn into Ar–Pd (aryl to the less hindered carbon); after bond rotation, syn β-hydride elimination releases the alkene and H–Pd–X; base removes HX to regenerate Pd(0).
由来Origin
沟吕木勉（1971）和理查德·赫克（1972）分别独立报道。赫克因此共获 2010 年诺贝尔化学奖。
Reported independently by Tsutomu Mizoroki (1971) and Richard Heck (1972); Heck shared the 2010 Nobel Prize in Chemistry.
特点与应用Features and uses
不需要预先制备有机金属试剂；缺电子烯烃（丙烯酸酯、苯乙烯）反应最好。分子内赫克反应和不对称赫克反应可构建季碳中心与复杂环系，用于萘普生、孟鲁司特等药物的合成。
No preformed organometallic reagent is needed; electron-poor alkenes (acrylates, styrenes) work best. Intramolecular and asymmetric Heck reactions build quaternary centres and ring systems, used in syntheses of naproxen and montelukast.
反应Reactions
Pd(OAc)₂/PPh₃ 或无膦条件，Et₃N 或 K₂CO₃，DMF 或 MeCN，80–140 °C
Pd(OAc)₂/PPh₃ or phosphine-free conditions, Et₃N or K₂CO₃, DMF or MeCN, 80–140 °C
氧化加成。
Oxidative addition.
烯烃配位与顺式迁移插入。
Alkene coordination and syn migratory insertion.
β-氢消除释放产物。
β-Hydride elimination releases the product.
碱促进的还原消除再生 Pd(0)。
Base-assisted reductive elimination regenerates Pd(0).
合成肉桂酸甲酯。
Synthesis of methyl cinnamate.
年表Timeline
- 1971
沟吕木报道钯催化芳基化烯烃
Mizoroki reports Pd-catalysed alkene arylation
- 1972
赫克独立报道并发展该反应
Heck independently reports and develops it
- 2010
赫克共获诺贝尔化学奖
Heck shares the Nobel Prize in Chemistry