烯烴交叉復分解反應

烯烴交叉復分解反應是指兩種端基烯烴在Ru(II)-卡賓(Grubbs Catalyst)催化下，放出乙烯的烯烴復分解反應。從統計學來看，反應應該生成三種可能的幾何異構體，再加上每種異構體各有 E/Z構型，因此共有六種產物。

此反應的選擇性近期得到更進一步的研究，有各種反應實例表明不同反應活性的烯烴都能高產率和高選擇性的反應。

烯烴復分解反應，按照反應過程中分子骨架的變化，可以分為五種情況：開環復分解、開環復分解聚合、非環二烯復分解聚合、關環復分解以及交叉復分解反應。

在1990年代， Robert H.Grubbs發現了實用性非常高的催化劑。之后烯烴復分解反應成為有機合成化學里最常用的反應之一。

常見的催化劑：

此反應的后處理，很多文獻報道的都是反應結束以后，直接濃縮干再做進一步處理。但是實際操作中卻發現，直接濃縮的過程中往往會造成新的雜質。這主要是由于Grubbs催化劑仍有活性，造成開環副產物，或者造成其他的烯烴復分解副反應。因此，反應結束以后及時淬滅（或失活）Grubbs催化劑是非常必要的。OL報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】。

反應機理：

引發:

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

反應實例：

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

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

二、化學空間: 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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