Nucleophilic attack on carbonyls

Next to tetrahedral systems, trigonal systems are considered as reaction centres in Baldwin s rules. These predict that 3- to 1-exo-trig reactions are all favoured processes. Very accurate EM s have been reported by Bruice and Benkovic (1963) for intramolecular nucleophilic attack on carbonyl in [39] and [40]. When Ar is varied from C6H5 to p-NOzC6H4, the EM of [39]... 

Nucleophilic attack on carbonyl group 86 - 90 on phosphoryl and sulfuryl groups 89,90,260-266 on saturated carbon 90,91 Nucleophilic catalysis 61, 84, 85 examples with enzymes 45, 85, 100, 101,311... 

A. J. Stone and R. W. Erskine, J. Am. Chem. Soc., 102, 7185 (1980). Intermolecular Self-Consistent-Field Perturbation Theory for Organic Reactions. 1. Theory and Implementation Nucleophilic Attack on Carbonyl Compounds. 

Addition appears to involve nucleophilic attack on carbonyl carbon by the strongly basic cyanide ion subsequently (or possibly simultaneously) oxygen accepts a hydrogen ion to form the cyanohydrin product ... 

Nucleophilic attack on carbonyl What controls the rates of reactions How mechanisms are discovered ch41... 

CYCLIZATION REACTIONS INVOLVING NUCLEOPHILIC ATTACK ON CARBONYL DERIVATIVES 734... 

The important part of TPP is the five-membered ring, in which a carbon is found between a nitrogen and a sulfur. This carbon forms a carbanion and is extremely reactive, making it able to perform a nucleophilic attack on carbonyl groups, leading to decarboxylation of several compounds in different pathways. 

Nucleophilic attack on carbonyl groups leaving group Kinetics and mechanism chi 2... 

Transesterification reactions could occur during anionic ROP of six-membered carbonates (Scheme 4.5). The intramolecular nucleophilic attack on carbonyl carbon atom (back-biting) leads to cyclic oligomers. The control of the polymerisation is rather poor, and bimodal distribution of molar masses is often observed (Matsuo et al., 1998b Pahovnik and Hadjichristidis, 2015). 

Unsaturated Esters.— An easy route to a)3-unsaturated esters has a nucleophilic attack on carbonyls by anions derived from O-ethyl 5-ethoxycarbonylmethyl dithiocarbonate and thiocarbonate, as its key step (Scheme 44). Yields are high and the method appears to have general application. An alternative approach to such compounds, due to Zweifel and Lynd, entails reaction between chloro-formates and vinylalanes, derived from terminal acetylenes and di-isobutylalu-minium hydride yields are better than 60%. 

Related catalytic processes are discussed elsewhere (Chapter 14) as are intramolecular ligand rearrangements (Chapter 13). Quantitative studies of nucleophilic attack on carbonyl ligands are also generally outside the scope of this chapter, and are discussed only where attack at carbon monoxide occurs competitively with reaction at a coordinated hydrocarbon. A short section on nucleophilic attack at coordinated isocyanides is included for the first time. 

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