Multicomponent Petasis reaction

N. A. Petasis, Multicomponent reactions with organoboron compounds, in Multicomponent Reactions, 1st Edition (Eds. J. Zhu and H. Bienayme), John Wiley Sons, Ltd, Weinheim (2005), pp. 199-223. 

Petasis N (2005) Multicomponent reactions with organoboron compounds. In Zhu J, Bienayme H (eds) Multicomponent reactions. Wiley-VCH, Weinheim, pp 199-223... 

The Petasis Reaction is a multicomponent reaction (MCR) that enables the preparation of amines and their derivatives such as 01-amino acids. 

The Petasis reaction is a mild multicomponent reaction that allows the conden sation of a boronic acid, an amine, and a carbonyl derivative to generate an allylic amine. Although several diastereoselective Petasis reactions have been reported [106], the first catalytic asymmetric reaction was described in 2008 (Scheme 1.29) [107]. It was shown that the condensation proceeds in high yields and enantiomeric excesses, affording the corresponding protected a vinylglycine derivatives. 

One may consider the Strecker reaction as the prototypical multicomponent reaction.15 Three reactants, an amine, a carbonyl compound, and a source of cyanide, come together in a single reaction vessel to afford a single product, an a-aminonitrile. Variations on this reaction process include the Bucherer-Bergs, Petasis, Ugi, and amidocarbonylation reactions. 

Candeias NR, Montalbano F, Cal PMSD et al (2010) Boronic Acids and Esters in the Petasis-Borono Mannich Multicomponent Reaction. Chem Rev 110 6169-6193... 

See, for instances (a) S. Santra, R R. Andreana, Org. Lett. 2007, 9, 5035-5038. A one-pot, microwave-influenced synthesis of diverse small molecules by multicomponent reaction cascades, (b) M. Presset, Y. Coquerel, J. Rodriguez, Org. Lett. 2009, 11, 5706-5709. Microwave-assisted domino and multi-component reactions with cyclic acyUcetenes expeditious syntheses of oxazinones and oxazindiones. (c) W.-J. Hao, B. Jiang, S.-J. Tu, X.-D. Cao, S.-S. Wu, S. Yan, X.-H. Zhang, Z.-G. Han, F. Shi, Org. Biomol. Chem. 2009, 7,1410-1414. A new mild base-catalyzed Mannich reaction of hetero-arylamines in water highly efficient stereoselective synthesis of 3-aminoketones under microwave heating, (d) P. Nun, J. Martinez, F. Lamaty, Synthesis 2010, 2063-2068. Microwave-assisted neat procedure for the Petasis reaction. 

As mentioned previously in this book, the quest for sustainable, atom-economical, and environmentally friendly chemical processes is a big current issue. Besides one-pot, sequential reaction processes (generally catalyzed by either metals or enzymes), multicomponent reactions have become very important [51]. The Petasis reaction, alternatively called Petasis horono Mannich reaction, is a mUd multicomponent reaction, which was reported first by Petasis and Akritopoulou in 1993 [52]. This reaction allows the one-pot three-component condensation of an aryl- or alkylboronic acid, an amine, and an aldehyde (or generally a carbonylic compound) to generate substituted amines at room temperature (Scheme 6.38). 

Synthetic highlights The synthesis of 1,2-DQs exemplifies asymmetric organo-catalysis in which enantioselective synthetic reactions are catalyzed by small organic molecules. To generate 1,2-DQs, achiral thiourea and axially chiral biphenols are used as catalysts for the enantioselective Petasis reaction. This is an illustration of a multicomponent reaction (MCR), for which the general concept and examples are also described. 

A two-step Petasis-deprotection-cyclodehydration-oxidation sequence was reported by Ayaz et al. [62], which enables the preparation of quinoxaline congeners in rapid fashion (Scheme 40). The use of MW irradiation diminishes the reaction time of the usual Petasis reaction making this multicomponent reaction more attractive. The Petasis... 

Organoboron compounds have gained special attention and importance in the last years due to their use in different processes, but one of the most important and efficient protocols is the multicomponent Petasis-borono-Mannich (PBM) reaction [17-19]. In this approach, an amine, an aldehyde, and a boronic acid react to give access to a new amine... 

FTY 720 440 is synthesized by a three-multicomponent Petasis reaction involving benzylamine 437, glycerine 438, and boronic acid 439 (Scheme 6.67). The desired product is obtained in 50% yield, which is further hydrogenated to FTY 720 (Gilenya ) 440 (45% yield over 2 steps) [135]. The latter is a clinically investigated immunosuppressive and shows also promising clinical results in the treatment of multiple sclerosis. 

In this chapter that highlights the synthesis of arylamines, we will discuss the most recent and relevant developments in the catalytic arylations of imine substrates, which incidentally are mostly enantioselective. The application of organomet2Jlic cat2dysts bearing Pd, Rh, Ru, and other metal catalysts will be considered, as well as the recent multicomponent Petasis reaction. 

The Petasis reaction is a multicomponent condensation occurring between boronic acids, amines and aldehydes. The asymmetric version of this reaction is very attractive for the synthesis of chiral a-amino acids.In this context, Schaus and Lou reported the use of chiral biphenols as organocatalysts for the asymmetric Petasis reaction of ( )-diethyl styrylboronate with secondary amines and ethyl glyoxylate. The corresponding a-amino esters were obtained in high yields and enantioselectivities of up to 97% ee by using a vaulted biaryl phenol such as (5)-VAPOL as the organocatalyst in the presence of 3-A molecular sieves (Scheme 2.59). 

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