The metal-catalyzed asymmetric conjugate addition (ACA) reaction has emerged as a general and powerful approach for the construction of optically active compounds and is among the most significant and useful reactions in synthetic organic chemistry In recent years, great progress has been made in this area with the use of various chiral metal complexes based on different chiral ligands This review provides comprehensive and critical information on the enantioselective 1,4-conjugate addition of nonorganometallic (soft) nucleophiles and their importance in synthetic applications The literature is covered from the last 10 years, and a number of examples from before 2007 are included as background information The review is divided into multiple parts according to the type of nucleophile involved in the reaction (such as C-, B-, O-, N-, S-, P-, and Si-centered nucleophiles) and metal catalyst systems used

Recent Advances in Metal-Catalyzed Asymmetric 1,4-Conjugate Addition (ACA) of Nonorganometallic Nucleophiles.

This review is devoted to the scientific achievements of the departments of organic chemistry in higher schools of Russia within the past decade.

Modern Trends of Organic Chemistry in Russian Universities

Molecular design, synthesis and biological evaluation of cage compound-based inhibitors of hepatitis C virus p7 ion channels.

Achieving high enantioselectivity and diastereoselectivity simultaneously­ is a rather challenging task for asymmetric catalytic synthesis­. Thanks to the rapid development of asymmetric transition-metal catalysis, significant progress has been made during recent years in achieving highly enantio- and diastereoselective conjugate addition reactions with a diverse combination of Michael donors and acceptors. This short review surveys the advances in transition-metal-catalyzed asymmetric diastereoselective Michael addition including diastereodivergent catalysis developed between 2015 and 2019. The review is divided into multiple parts according to the type of nucleophiles involved in the reaction. 1 	Introduction 2 	Addition of Functionalized Ketones and Dicarbonyl Compounds 3 	Addition of Aldimino Esters and Their Cyclic Analogues 4 	Addition of Indolin-2-ones 5 	Vinylogous Michael Reactions 6 	Other Michael Donors 7 	Cascade Reactions Initiated by Michael Addition 8 	Conclusion

Recent Developments in Highly Stereoselective Michael Addition Reactions Catalyzed by Metal Complexes

A mild transition-metal-free protocol to prepare 2,3-dialkylated tartaric acid esters has been developed by taking advantage of a visible light photoredox-catalyzed reductive dimerization of α-ketoesters with a combination of an organic dye photocatalyst and a Hantzsch-type 1,4-dihydropyridine hydrogen donor. A broad range of functional groups including cyclopropane, alkene, alkyne, 4-methoxybenzyl ether, acetal, silyl ether, carbamate, cyclic ether, cyclic thioether, bromoalkane, and N-alkoxyphthalimide are well-compatible. By employing the visible light photoredox-catalyzed reductive coupling and the subsequent optical resolution, both enantioenriched diastereomers of 2,3-dialkylated tartaric acid could be acquired conveniently.

http://pubs.acs.org/doi/pdf/10.1021/acsomega.7b00749

Synthesis of 2,3-Dialkylated Tartaric Acid Esters via Visible Light Photoredox-Catalyzed Reductive Dimerization of α-Ketoesters

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

Transition metal catalyzed asymmetric Michael additions of dimethyl (2-oxo-2-phenylethyl)phosphonate to a variety of aromatic nitroalkenes have been developed The effects of ligand structure, metal ions, and solvent on the reaction are described Ni(II)–bis[(1R,2R)-N,N′-dibenzylcyclohexane-1,2-diamine]Br2 was found to be an effective catalyst for this reaction The corresponding adducts were obtained in the presence of this complex in good yields and with excellent enantioselectivity (up to 99% ee) The absolute configurations of the reaction products were determined by X-ray diffraction

Asymmetric Michael additions of a β-oxophosphonate to nitroalkenes in the presence of chiral diamine complexes

Polyfunctional chiral phosphonates are of interest as intermediates in the synthesis of bioactive molecules [1–5]. A possible approach to preparation of these compounds is asymmetric addition of β-oxophosphonates to nitroalkenes [6]. Earlier, we have shown that complexes of nickel [7], cobalt, and manganese [8] with chiral diamines are efficient catalysts for enantioselective addition of 1,3dicarbonyl compounds to nitroalkenes. This reaction has been used as a key step in synthesis of chiral amino acids showing neurotropic activity [9], and of alicyclic polyfunctional derivatives [10].

The first example of Ni(II)-catalyzed asymmetric addition of β-oxophosphonate to nitroalkene

Functionally substituted sulfones with stereogenic centers are valuable reagents in organic synthesis and key motifs in some bioactive compounds. The asymmetric Michael addition of β-ketosulfones to conjugated nitroalkenes in the presence of Ni(II) complexes with various chiral vicinal diamines was studied. This reaction provides convenient access to non-racemic 4-nitro-2-sulfonylbutan-1-ones with two stereocenters with high yield and excellent enantioselectivity (up to 99%). It has been established that the catalytic Michael reaction itself was carried out with high diastereoselectivity, but the Michael adducts may epimerize at the C-2 position at a significant rate. Conditions for the preparation of individual diastereomers were found.

https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-15-127.pdf

Synthesis of non-racemic 4-nitro-2-sulfonylbutan-1-ones via Ni(II)-catalyzed asymmetric Michael reaction of β-ketosulfones.

An efficient synthesis of (R)- and (S)-4-amino-3-(adamant-1-yl)butyric acids and (R)- and (S)-4-(adamant-1-yl)pyrrolidin-2-ones is presented. The synthetic strategy is based on asymmetric Michael addition of diethyl malonate to 1-(adamant-1-yl)-2-nitroethene using available Ni(II) complex as the catalyst. The procedures provide good to high enantioselectivity of Michael addition to sterically hindered nitroalkene and good yields of (R)- and (S)-enantiomers of 3-adamantyl substituted GABA.

Anastasiya E. Sibiryakova

Papers

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

Asymmetric Michael additions of a β-oxophosphonate to nitroalkenes in the presence of chiral diamine complexes

The first example of Ni(II)-catalyzed asymmetric addition of β-oxophosphonate to nitroalkene

Synthesis of non-racemic 4-nitro-2-sulfonylbutan-1-ones via Ni(II)-catalyzed asymmetric Michael reaction of β-ketosulfones.

Asymmetric Synthesis of Adamantyl GABA Analogues