Conjugate addition, organocatalysis catalysis

Michael-aldol reaction as an alternative to the Morita-Baylis-Hillman reaction 14 recent results in conjugate addition of nitroalkanes to electron-poor alkenes 15 asymmetric cyclopropanation of chiral (l-phosphoryl)vinyl sulfoxides 16 synthetic methodology using tertiary phosphines as nucleophilic catalysts in combination with allenoates or 2-alkynoates 17 recent advances in the transition metal-catalysed asymmetric hydrosilylation of ketones, imines, and electrophilic C=C bonds 18 Michael additions catalysed by transition metals and lanthanide species 19 recent progress in asymmetric organocatalysis, including the aldol reaction, Mannich reaction, Michael addition, cycloadditions, allylation, epoxidation, and phase-transfer catalysis 20 and nucleophilic phosphine organocatalysis.21... 

Alternatively, the iminium-activation strategy has also been apphed to the Mukaiyama-Michael reaction, which involves the use of silyl enol ethers as nucleophiles. In this context, imidazolidinone 50a was identified as an excellent chiral catalyst for the enantioselective conjugate addition of silyloxyfuran to a,p-unsaturated aldehydes, providing a direct and efficient route to the y-butenolide architecture (Scheme 3.15). This is a clear example of the chemical complementarity between organocatalysis and transition-metal catalysis, with the latter usually furnishing the 1,2-addition product (Mukaiyama aldol) while the former proceeds via 1,4-addition when ambident electrophiles such as a,p-unsaturated aldehydes are employed. This reaction needed the incorporation of 2,4-dinitrobenzoic acid (DNBA) as a Bronsted acid co-catalyst assisting the formation of the intermediate iminium ion, and also two equivalents of water had to be included as additive for the reaction to proceed to completion, which... 

Carbons and Carbon Supported Catalysts in Hydroprocessing 2 Chiral Sulfur Ligands Asymmetric Catalysis 3 Recent Developments in Asymmetric Organocatalysis 4 Catalysis in the Refining of Fischer-Tropsch Syncrude 5 Organocatalytic Enantioselective Conjugate Addition Reactions A Powerful Tool for the Stereocontrolled Synthesis of Complex Molecules... 

Since its rediscovery by MacMillan in 2000, iminium activation catalysis has become a key catalytic concept in organocatalysis. After initial work centered on cycloadditions, Michael additions became the main area of interest and it is now estabhshed as a general strategy for the asymmetric conjugate addition of nucleophiles to a,P-unsaturated compounds. 

Brpnsted acids have shown good-to-excellent levels of selectivity in C S bond formations. This chapter aims to review the stereoselectivity aspect of C—S bond formations that use commodity chemicals such as alkynes, alkenes, and alkanes. The stereoselective functionalization of alkynes is reviewed in section 1 using hydrothiolation, bisthiolation, and carbothiolation that necessitate transition metal and Brpnsted acid catalysis. The next section covers sulfethera-tion and conjugate addition reactions, where electron-rich and electron-poor alkenes are exploited under Lewis acid and Brpnsted acid catalysis. The last section is centered on the use of alkanes in the stereoselective 5-alkylation catalyzed by transition metal and organocatalysis. 

Iminium-based organocatalysis is somewhat less explored than enamine-based organocatalysis and has been mostly used in the activation of a,/S-conjugated aldehydes and ketones. Therefore, this type of catalysis has unsurprisingly been the subject of a limited number of studies under the umbrella of the metal-organic cooperative catalysis concept. In 2011, the Cdrdova group [55] reported the first enantioselective and chemoselective /3-silyl addition to a./S-unsaturated aldehydes using copper salts and chiral pyrrolidine derivatives as catalysts. As proposed, the chiral secondary amine forms an iminium salt with... 

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