相关反应
曼尼奇反应
多组分反应
Related Reactions
Mannich Reaction
Multicomponent Reactions
Petasis Reaction Petasis反应
Petasis反应是一种多组分反应(MCR),它能够制备胺及其衍生物,如α-氨基酸。
该反应也称为硼酸曼尼希反应,因为它通过亚胺与硼酸的有机配体作为亲核剂进行,类似于烯醇化酮组分在原始曼尼希反应中的作用。
Petasis反应机理
如同经典反应一样,Petasis反应也涉及许多相互依赖的平衡步骤,其中一些步骤与Mannich反应中的步骤相同。
关于从硼酸盐到亚胺的有机配体亲核加成的关键步骤,人们几乎不确定。一个建议是,转移实际上是分子内的,并通过如上图所示的加合物发生:
不管它是如何发生的,这个加法是不可逆的这一事实无疑给予了一个明显的优势。在经典Mannich中,最后一步的可逆性限制了产量综合有用的情况的数量。相比之下,硼酸-曼尼奇反应允许进行更广泛的转化。
与乙醛酸的直接反应值得特别提及,因为它在一个步骤中导致有趣的、非自然的α-氨基酸,同时避免了毒性副产物的出现,如Strecker合成。
这种反应可以在二氯甲烷中在室温下与仲胺、位阻伯胺、肼或苯胺发生反应。潜在亲核伙伴的范围包括烯基硼酸、电中性以及富电子(杂)芳基酸。在适当的溶剂中,在高温(mw)下可影响贫电子硼酸的转化(M. Follmann et al. Synlett 2005, 1009. DOI).
Recent Literature 近期文献
Petasis Boronic Mannich Reactions of Electron-Poor Aromatic Amines under Microwave Conditions
M. Follmann, F. Gaul, T Schäfer, S. Kopec, P. Hamley, Synlett, 2005, 1009-1011.
A Copper-Catalyzed Petasis Reaction for the Synthesis of Tertiary Amines and Amino Esters
R. Frauenlob, C. Carcía, G. A. Bradshaw, H. M. Burke, E. Bergin, J. Org. Chem., 2012, 77, 4445-4449.
A Palladium-Catalyzed Three-Component Synthesis of Arylmethylsulfonamides
T. Beisel, G. Manolikakes, Synthesis, 2016, 48, 379-386.
Component-Selective and Stereocontrolled One-Step Three-Component Reaction among Aldehydes, Amines, and Allenyl Boronic Acids or Allenyl Pinacolboronates
F. Liepouri, G. Bernasconi, N. A. Petasis, Org. Lett., 2015, 17, 1628-1631.
Mild and Catalyst-Free Petasis/Decarboxylative Domino Reaction: Chemoselective Synthesis of N-Benzyl Propargylamines
H. Feng, H. Jia, Z. Sun, J. Org. Chem., 2014, 79, 11812-11818.
Microwave-Assisted Neat Procedure for the Petasis Reaction
P. Nun, J. Martinez, F. Lamaty, Synthesis, 2010, 2063-2068.
Copper-Catalyzed Petasis-Type Reaction: A General Route to α-Substituted Amides From Imines, Acid Chlorides, and Organoboron Reagents
M. S. T. Morin, Y. Lu, D. A. Black, B. A. Arndtsen, J. Org. Chem., 2012, 77, 2013-2017.
Regioselective and Diastereoselective Borono-Mannich Reactions with Pinacol Allenylboronate
T. Thaima, S. G. Pyne, Org. Lett., 2015, 17, 778-781.
A Direct Synthesis of Allenes by a Traceless Petasis Reaction
D. A. Mundal, K. E. Lutz, R. J. Thomson, J. Am. Chem. Soc., 2012, 134, 5782-5785.
Enantioselective Synthesis of Allenes by Catalytic Traceless Petasis Reactions
Y. Jiang, A. B. Diagne, R. J. Thomson, S. E. Schaus, J. Am. Chem. Soc., 2017, 139, 1826-1829.
Synthesis of 1-Amino-1H-Indenes via a Sequential Suzuki-Miyaura Coupling/Petasis Condensation Sequence
V. Jayaram, T. Sridhar, G. V. M. Sharma, F. Berrée, B. Carboni, J. Org. Chem., 2017, 82, 1803-1811.