烯烃交叉复分解反应是指两种端基烯烃在Ru(II)-卡宾(Grubbs Catalyst)催化下,放出乙烯的烯烃复分解反应。从统计学来看,反应应该生成三种可能的几何异构体,再加上每种异构体各有 E/Z构型,因此共有六种产物。
此反应的选择性近期得到更进一步的研究,有各种反应实例表明不同反应活性的烯烃都能高产率和高选择性的反应。
烯烃复分解反应,按照反应过程中分子骨架的变化,可以分为五种情况:开环复分解、开环复分解聚合、非环二烯复分解聚合、关环复分解以及交叉复分解反应。
在1990年代, Robert H.Grubbs发现了实用性非常高的催化剂。之后烯烃复分解反应成为有机合成化学里最常用的反应之一。
常见的催化剂:
反应机理:
引发:
最新文献:
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. Kędziorek, K. Grela, Synlett, 2011, 124-128.
参考文献
一、https://www.organic-chemistry.org/namedreactions/cross-metathesis.shtm
二、化学空间: 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