烯烴交叉復(fù)分解反應(yīng)是指兩種端基烯烴在Ru(II)-卡賓(Grubbs Catalyst)催化下，放出乙烯的烯烴復(fù)分解反應(yīng)。從統(tǒng)計(jì)學(xué)來看，反應(yīng)應(yīng)該生成三種可能的幾何異構(gòu)體，再加上每種異構(gòu)體各有 E/Z構(gòu)型，因此共有六種產(chǎn)物。

此反應(yīng)的選擇性近期得到更進(jìn)一步的研究，有各種反應(yīng)實(shí)例表明不同反應(yīng)活性的烯烴都能高產(chǎn)率和高選擇性的反應(yīng)。

烯烴復(fù)分解反應(yīng)，按照反應(yīng)過程中分子骨架的變化，可以分為五種情況：開環(huán)復(fù)分解、開環(huán)復(fù)分解聚合、非環(huán)二烯復(fù)分解聚合、關(guān)環(huán)復(fù)分解以及交叉復(fù)分解反應(yīng)。

在1990年代， Robert H.Grubbs發(fā)現(xiàn)了實(shí)用性非常高的催化劑。之后烯烴復(fù)分解反應(yīng)成為有機(jī)合成化學(xué)里最常用的反應(yīng)之一。

常見的催化劑：

此反應(yīng)的后處理，很多文獻(xiàn)報(bào)道的都是反應(yīng)結(jié)束以后，直接濃縮干再做進(jìn)一步處理。但是實(shí)際操作中卻發(fā)現(xiàn)，直接濃縮的過程中往往會造成新的雜質(zhì)。這主要是由于Grubbs催化劑仍有活性，造成開環(huán)副產(chǎn)物，或者造成其他的烯烴復(fù)分解副反應(yīng)。因此，反應(yīng)結(jié)束以后及時(shí)淬滅（或失活）Grubbs催化劑是非常必要的。OL報(bào)道了一種非常高效失活并移除Grubbs催化劑的方法，即使用Ph3PO或DMSO處理以后加快速柱的方式【Org. Lett., 2001, 3, 1413】。

反應(yīng)機(jī)理：

引發(fā):

【Strategic Applications of Named Reactions in OrganicSynthesis, László Kürti and Barbara Czakó, page 10.】

反應(yīng)實(shí)例：

Rate Enhanced Olefin Cross-Metathesis Reactions: The Copper Iodide Effect
K. Voigtritter, S. Ghorai, B. H. Lipshutz, J. Org. Chem., 2011, 76, 4697-4702.

Olefin Cross-Metathesis Reactions at Room Temperature Using the Nonionic Amphiphile “PTS”: Just Add Water
B. H. Lipshutz, G. T. Aquinaldo, S. Ghorai, K. Voigtritter, Org. Lett., 2008, 10, 1325-1328.

Increased Efficiency in Cross-Metathesis Reactions of Sterically Hindered Olefins
I. C. Stewart, C. J. Douglas, R. H. Grubbs, Org. Lett., 2008, 10, 441-444.

Acryloyl Chloride: An Excellent Substrate for Cross-Metathesis. A One-Pot Sequence for the Synthesis of Substituted α,β-Unsaturated Carbonyl Derivatives
L. Ferrié, S. Bouzbouz, J. Cossy, Org. Lett., 2009, 11, 5446-5448.

A Rapid and Simple Cleanup Procedure for Metathesis Reactions
B. R. Galan, K. P. Kalbarczyk, S. Szczepankiewicz, J. B. Keister, S. T. Diver, Org. Lett., 2007, 9, 1203-1206.

Regioselective Cross-Metathesis Reaction Induced by Steric Hindrance
S. BouzBouz, R. Simmons, J. Cossy, Org. Lett., 2004, 6, 3465-3467.

An Efficient Synthesis of Nitroalkenes by Alkene Cross Metathesis: Facile Access to Small Ring Systems
G. P. Marsh, P. J. Parsons, C. McCarthy, X. G. Corniquet, Org. Lett., 2007, 9, 2613-2616.

Selective Synthesis of (2Z,4E)-Dienyl Esters by Ene-Diene Cross Metathesis
G. Moura-Letts, D. P. Curran, Org. Lett., 2007, 9, 5-8.

Advanced Fine-Tuning of Grubbs/Hoveyda Olefin Metathesis Catalysts: A Further Step toward an Optimum Balance between Antinomic Properties
M. Bieniek, R. Bujok, M. Cabaj, N. Lugan, G. Lavigne, D. Arlt, K. Grela, J. Am. Chem. Soc., 2006, 128, 13652-13653.

A Good Bargain: An Inexpensive, Air-Stable Ruthenium Metathesis Catalyst Derived from α-Asarone
K. Grela, M. Kim, Eur. J. Org. Chem., 2003, 963-966.

The facile preparation of alkenyl metathesis synthons
T. W. Baughman, J. C. Sworen, K. B. Wagener, Tetrahedron, 2004, 60, 10943-10948.

Ruthenium-Catalyzed Tandem Olefin Metathesis-Oxidations
A. A. Scholte, M. H. An, M. L. Snapper, Org. Lett., 2006, 8, 4759-4762.

Ruthenium-Catalyzed Tandem Cross-Metathesis/Wittig Olefination: Generation of Conjugated Dienoic Esters from Terminal Olefins
R. P. Murelli, M. L. Snapper, Org. Lett., 2007, 9, 1749-1752.

Preparation of Aliphatic Ketones through a Ruthenium-Catalyzed Tandem Cross-Metathesis/Allylic Alcohol Isomerization
D. Finnegan, B. A. Seigal, M. L. Snapper, Org. Lett., 2006, 8, 2603-2606.

Heteroaromatic Synthesis via Olefin Cross-Metathesis: Entry to Polysubstituted Pyridines
T. J. Donohoe, J. A. Basutto, J. F. Bower, A. Rathi, Org. Lett., 2011, 13, 1036-1039.

Cross Metathesis of N-Allylamines and α,β-Unsaturated Carbonyl Compounds: A One-Pot Synthesis of Substituted Pyrroles
S. Shafi, M. K?dziorek, K. Grela, Synlett, 2011, 124-128.

參考文獻(xiàn)

一、https://www.organic-chemistry.org/namedreactions/cross-metathesis.shtm

二、化學(xué)空間: https://cn.chem-station.com/reactions/2014/01/%e7%83%af%e7%83%83%e5%a4%8d%e5%88%86%e8%a7%a3%e5%8f%8d%e5%ba%94%ef%bc%88olefin-metathesis%ef%bc%89.html

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