There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

[신간의 별자리x] 우리/미술, 그리고 ‘슬픔의 박물관’

Ru-, Rh-, and Pd-Catalyzed C-C Bond Formation Involving C-H Activation and Addition on Unsaturated Substrates: Reactions and Mechanistic Aspects

Catalytic C–H activation has emerged as a powerful tool for sustainable syntheses. In the recent years, notable success was achieved with the development of cobalt-catalyzed C–H functionalizations with either in situ generated or single-component cobalt-complexes under mild reaction conditions. Herein, recent progress in the field of organometallic cobalt-catalyzed C–H activation is reviewed until November 2015.

Cobalt-Catalyzed C―H Activation

The development of new methods for the direct functionalization of unactivated C–H bonds is ushering in a paradigm shift in the field of retrosynthetic analysis. In particular, the catalytic enantioselective functionalization of C–H bonds represents a highly atom- and step-economic approach toward the generation of structural complexity. However, as a result of their ubiquity and low reactivity, controlling both the chemo- and stereoselectivity of such processes constitutes a significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation. Our analysis serves to document the considerable and rapid progress within in the field, while also highlighting limitations of current methods.

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Catalytic Enantioselective Transformations Involving C-H Bond Cleavage by Transition-Metal Complexes.

Stereoselective Electrocatalytic Transformations of Malononitrile and Aromatic Aldehydes into (1R,5S,6R)*‐4,4‐Dialkoxy‐2‐amino‐6‐aryl‐1,5‐dicyano‐3‐azabicyclo [3.1.0]hex‐2‐enes.

A mechanically activated solid-state reaction of halogenation of naphthalene with a Pb(OAc)4—alkaline or alkaline-earth metal halide system was carried out to yield 1-halonaphthalene as the main reaction product and 1,4-dihalonaphthalene. The solid-state halogenation of naphthalene is more selective than a liquid-phase reaction.

solid-state reaction of a lead tetraacetate-metal halide system with naphthalene under mechanical activation

1.

The kinetics of the decomposition of tertiary butyl hydroperoxide and the rate of generation of free radicals from it at 130° in methyl caproate and its chlorobenzene solutions was studied.




2.

In thermal decomposition in esters, tert-butyl hydroperoxide decomposes chiefly through its acylation by the ester, followed by homolysis of the intermediate perester formed.

Mechanism of the thermal decomposition of tertiary butyl hydroperoxide in esters

1.

We synthesized the esters of some peroxydicarboxylic acids\({\text{CH}}_{\text{3}} {\text{OOC(CH}}_{\text{2}} {\text{)}}_n \mathop {\text{C}}\limits^{\mathop {{\text{||}}}\limits^{\text{O}} } {\text{OO}}\mathop {\text{C}}\limits^{\mathop {{\text{||}}}\limits^{\text{O}} } {\text{(CH}}_{\text{2}} {\text{)}}_n {\text{COOCH}}_{\text{3}} \), and determined the kinetic parameters of the reaction for their thermal decomposition in CH3COOH and benzene. The predominant generation of CH3OOC(CH2). n radicals occurs in the decomposition of the lower homologs (n=2,3), while the\({\text{CH}}_{\text{3}} {\text{OOC(CH}}_{\text{2}} {\text{)}}_n \mathop {\text{C}}\limits^{\mathop {{\text{||}}}\limits^{\text{O}} } {\text{O}}\) radicals are obtained mainly from the higher homologs (n=6,8).




2.

A new homolytic cyclization reaction was discovered, namely the formation ofγ-butyrolactone from theγ-carbomethoxypropyl radicals that are obtained during the decomposition of the dimethyl ester of peroxydiglutaric acid.

G. I. Nikishin

Papers

Stereoselective Electrocatalytic Transformations of Malononitrile and Aromatic Aldehydes into (1R,5S,6R)*‐4,4‐Dialkoxy‐2‐amino‐6‐aryl‐1,5‐dicyano‐3‐azabicyclo [3.1.0]hex‐2‐enes.

solid-state reaction of a lead tetraacetate-metal halide system with naphthalene under mechanical activation

Mechanism of the thermal decomposition of tertiary butyl hydroperoxide in esters

Thermal decomposition of esters of peroxydicarboxylic acids

Oxidizing 1,3-cyclization of alkyl radicals