Recent Developments in Enantioselective Metal‐Catalyzed Domino Reactions

Abstract

International audienceThis review updates the major progress in the field of enantioselective one-, two-, and multicomponent domino reactions promoted by chiral metal catalysts, covering the literature since the beginning of 2012. It illustrates how enantioselective metal-catalyzed processes have emerged as outstanding tools for the development of a wide variety of fascinating one-pot asymmetric domino reactions, allowing complex and diverse structures to be easily generated from simple materials in a single step. During the last 4 years, a myriad of already existing as well as completely novel and powerful asymmetric domino processes have been developed on the basis of asymmetric metal catalysis, taking economical advantages, such as avoiding costly protecting groups and time-consuming purification procedures after each step

Nitroalkenes in the Ni(II) Catalyzed AsymmetricMichaelAddition. Convenient Route to the Key Intermediate of Brivaracetam

“…Metal catalyzed asymmetric Michael addition is an effective strategy for the total synthesis of natural compounds [1] and is used as the initial stage of a series of cascade transformations. [2][3][4][5] The reaction of 1,3dicarbonyl compounds with nitroalkenes attracts the greatest attention, since the resulting adducts suggest a wide range of possible further applications, the most important of which is the reductive cyclization as the way to pyrrolidine-2-ones and gamma-amino acids. [6,7] A number of these compounds are used as drugs for the treatment of CNS disorders ((R)-baclofen 1, [8 -10] (R)-rolipram 2, [11,12] and (S)-pregabalin 3 [13 -18] (Figure 1)).…”

“…1 H-NMR (400 MHz, CDCl 3 ): 2.47 (br. s, 2 NH); 3.46 (d,2 J HH = 13.3, CH 2 ); 3.64 (d, 2 J HH = 13.3, CH 2 ); 3.70 (s, 2 CH); 6.93 -6.99 (m, 4 H); 7.04 -7.07 (m, 4 H); 7.14 -7.20 (m, 10 H) 13. C-NMR (100.5 MHz, CDCl 3 ): 50.64 (s, CH 2 ); 68.21 (s, CH); 115.19 (d, 2 J CF = 21.1, CH); 127.18 (s, CH); 127.99 (s, CH); 128.17 (s, CH); 129.73 (d, 3 J CF = 7.7, CH); 136.11 (s, C); 140.85 (s, C); 161.95 (d, 1 J CF = 244.4, CÀ F).…”

Easy Access to Enantiopure (S)‐ and (R)‐Aryl Alkyl Alcohols by a Combination of Gold(III)‐Catalyzed Alkyne Hydration and Enzymatic Reduction

“…[1][2][3] In this regard, the combination of several reaction steps within one poti sa na ttractive strategy,a st he number of workup and purification steps can be substantially reduced. [4][5][6][7][8][9] During the past decades, biocatalysis was established as ah ighly potent method for the introductiona nd manipulation of stereochemistry,i n particularo nt he basis of improved access to versatile enzymes of naturalo rigin or by enzyme engineering. [10][11][12][13][14][15] Linking enzyme-mediated reactions with metal-assisted catalysis is generallyu nderstooda sahighly prospective approach, as both areas offer complementary functional group interconversions.…”

A facile base-promoted domino Michael/O-alkylation reaction for the construction of succinimide-substituted 3(2H)-furanones

“…Domino reactions are one of the most efficient strategies for the synthesis of complex molecular structures from simple materials in a single step. [17][18][19][20] Recently, γ-halogenated-β-ketoesters, which are commercially available, were used to construct substituted 3(2H)-furanones via domino reactions with activated alkenes [21][22][23] and imines. [24][25][26] This synthetic strategy is efficient and mild.…”