贝利斯-希尔曼反应_Baylis-Hillman Reaction
活化烯烃衍生物与醛的偶联是由叔胺(例如：DABCO=1,4-二氮杂双环[2.2.2]辛烷)催化的。磷化氢也可以用于该反应，如果胺或磷化氢催化剂不对称，则可以进行对映选择性反应。
Baylis-Hillman反应机理
关键步骤是在活化烯烃中加入胺催化剂以形成稳定的亲核阴离子。这种原位生成的亲核试剂然后添加到醛中。随后消除催化剂导致观察到的产物。
其他活化氮亲核试剂也可能是合适的，DMAP和DBU在某些情况下优于DABCO：
添加DBU和甲基丙烯酸酯的产物
对于在极性，非极性和质子条件下的芳基醛，已经确定速率确定步骤在DABCO和丙烯酸酯中在醛和一级中是二级的。 根据该反应速率数据，Tyler McQuade最近提出了（J.Org.Chem.2005,70,3980。DOI）以下涉及形成半缩醛中间体的机制：
Recent Literature 近期文献
Octanol-Accelerated Baylis-Hillman Reaction
K.-S. Park, J. Kim, H. Choo, Y. Chong, Synlett, 2007, 395-398.
The First One-Pot Synthesis of Morita-Baylis-Hillman Adducts Starting Directly from Alcohols
L. D. S. Yadav, V. P. Srivasta, R. Patel, Synlett, 2010, 1047-1050.
Dramatic Rate Acceleration of the Baylis-Hillman Reaction in Homogeneous Medium in the Presence of Water
J. Cai, Z. Zhou, G. Zhao, C. Tang, Org. Lett., 2002, 4, 4723-4725.
Synthesis of 1,3-Dialkyl-1,2,3-triazolium Ionic Liquids and Their Applications to the Baylis-Hillman Reaction
Y. Jeong, J.-S. Ryu, J. Org. Chem., 2010, 75, 4183-4191.
Sila-Morita-Baylis-Hillman Reaction of Arylvinyl Ketones: Overcoming the Dimerization Problem
A. Trofimov, V. Gevorgyan, Org. Lett., 2009, 11, 253-255.
A Highly Active and Selective Catalyst System for the Baylis-Hillman Reaction
J. You, J. Xu, J. G. Verkade, Angew. Chem. Int. Ed., 2003, 41, 5054-5066.
Traditional Morita-Baylis-Hillman reaction of aldehydes with methyl vinyl ketone co-catalyzed by triphenylphosphine and nitrophenol
M. Shi, Y.-H. Liu, Org. Biomol. Chem., 2006, 4, 1468-1470.
Succesful Baylis Hillman Reaction of Acrylamide with Aromatic Aldehydes
C. Yu, L. Hu, J. Org. Chem., 2002, 67, 219-223.
Ionic Liquid-Immobilized Quinuclidine-Catalyzed Morita-Baylis-Hillman Reactions
X. Mi, S. Luo, J.-P. Cheng, J. Org. Chem., 2005, 70, 2338-2341.
Morita-Baylis-Hillman Reaction of α,β-Unsaturated Ketones with Allylic Acetates by the Combination of Transition-Metal Catalysis and Organomediation
Y.-Q. Li, H.-J. Wang, Z.-Z. Huang, J. Org. Chem., 2016, 81, 4429-4433.
Guanidine-Catalyzed γ-Selective Morita-Baylis-Hillman Reactions on α,γ-Dialkyl-Allenoates: Access to Densely Substituted Heterocycles
P. Selig, A. Turočkin, W. Raven, Synlett, 2013, 24, 2535-2539.
A Practical Preparation of 2-Hydroxymethyl-2-cyclopenten-1-one by Morita-Baylis-Hillman Reaction
H. Ito, Y. Takenaka, S. Fukunishi, K. Iguchi, Synthesis, 2005, 3035-3038.
Acceleration of the Morita-Baylis-Hillman Reaction by a Simple Mixed Catalyst System
A. Bugarin, B. T. Connell, J. Org. Chem., 2009, 74, 4638-4641.
Asymmetric Morita-Baylis-Hillman Reactions Catalyzed by Chiral Brønsted Acids
N. T. McDougal, S. E. Schaus, J. Am. Chem. Soc., 2003, 125, 12094-12095.
MgI2-accelerated enantioselective Morita-Baylis-Hillman reactions of cyclopentenone utilizing a chiral DMAP catalyst
A. Bugarin, B. T. Connell, Chem. Commun., 2010, 46, 2644-2646.
Catalytic Asymmetric Aza-Morita-Baylis-Hillman Reaction of Methyl Acrylate: Role of a Bifunctional La(O-iPr)3/Linked-BINOL Complex
T. Yukawa, B. Seelig, Y. Xu, H. Morimoto, Y. Xu, H. Morimoto, S. Matsunaga, A. Berkessel, M. Shibasaki, J. Am. Chem. Soc., 2010, 132, 11988-11992.
Chiral Bifunctional Organocatalysts in Asymmetric Aza-Morita-Baylis-Hillman Reactions of Ethyl (Arylimino)acetates with Methyl Vinyl Ketone and Ethyl Vinyl Ketone
M. Shi, G.-N. Ma, J. Gao, J. Org. Chem., 2007, 72, 9779-9781.
A Brønsted Acid and Lewis Base Organocatalyst for the Aza-Morita-Baylis-Hillman Reaction
K. Matsui, S. Takizawa, H. Sasai, Synlett, 2006, 761-765.
Organocatalytic Tandem Three-Component Reaction of Imine, Alkyl Vinyl Ketone, and Imide via aza-Baylis-Hillman Reaction
S.-e. Syu, Y.-T. Lee, Y.-J. Jang, W. Lin, J. Org. Chem., 2011, 76, 2888-2891.
Organocatalysis of the Morita-Baylis-Hillman Alkylation Using Trialkylphosphines
M. E. Krafft, K. A. Seibert, Synlett, 2006, 3334-3336.