Metal-catalysed cleavage of carbon-carbon bonds

Reactions cleaving carbon-carbon bonds with the assistance of transition metals as the catalyst have provided various molecular transformations that are otherwise difficult to execute, opening a scenic avenue along organic synthesis. Construction of structural motifs like medium-sized carbocycles and chiral quaternary carbon centres have been set within an access of such paradoxical approaches in the past decade.     

Silylzincation of carbon-carbon multiple bonds revisited

The first investigation of the copper-catalyzed silylzincation of alkynes as well as a diene and styrene using bis(triorganosilyl) zinc reagents led to the development of an efficient procedure and the disclosure of an unexpected bissilylation and unforeseen regioselectivity.     

Asymmetric hydroamination of non-activated carbon-carbon multiple bonds

The catalysed enantioselective formation of carbon-nitrogen bonds by the hydroamination reaction is reviewed. All examples deal with substrates containing non-activated carbon-carbon multiple bonds which are transformed either via intramolecular or intermolecular reactions. Structurally different complexes already provided nitrogen containing compounds/heterocycles with high enantioselectivities.     

Metal-catalyzed additions of H-P(O) bonds to carbon-carbon unsaturated bonds

In this short review, we briefly summarize our studies on metal-catalyzed additions of H-P(O) bonds to carbon-carbon unsaturated compounds (alkynes, alkenes, allenes, dienes and related). These new reactions provide regio- and stereoselective ways for the preparation of a variety of organophosphorus compounds. Mechanistic aspects related to the catalytic processes are discussed.     

Stannylation of unsaturated carbon-carbon bonds by tin tetrachloride

The reactions of tin tetrachloride and four terminal alkynes (PhCCH, ^tBuCCH, ⁿBuCCH, HOCH₂CCH), norbornene, and norbornadiene in dichloromethane or chloroform solution lead to the formation of stannylation products, which were characterized by ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Virtually complete α-regioselectivity was obtained in reaction of all four alkynes without any effect of the relative steric bulk of the substituent R at the triple bond of alkyne RC_βC_αH. The reaction of norbornene and norbornadiene with SnCl₄ is stereoselective, giving an exo stannylation product.     

Bond ionicity and the strength of carbon-carbon bonds

A simple VB analysis is used to illustrate that the greater stability of geminally disubstituted ethanes and ethylenes compared to their vicinally substituted counterparts is due to the strength of the central C-C bond and not to the stability of the radical and carbene fragments that compose the molecule. The qualitative arguments are supported by MO calculations. The implications to the additivity rules for the estimation of heats of formation are discussed.     

Reduction of carbon-carbon double bonds using organocatalytically generated diimide

An efficient method has been developed for the reduction of carbon-carbon double bonds with diimide, catalytically generated in situ from hydrazine hydrate. The employed catalyst is prepared in one step from riboflavin (vitamin B(2)). Reactions are carried out in air and are a valuable alternative when metal-catalyzed hydrogenations are problematic.     

Addition of ArSSAr to carbon-carbon multiple bonds using electrochemistry

ArS(ArSSAr)⁺ (arylbis(arylthio)sulfonium ions), which were generated and accumulated by the electrochemical oxidation of diaryl disulfides (ArSSAr) in CH₂Cl₂ at −78 °C, reacted with alkenes to give the corresponding diarylthio-substituted compounds in a stereospecific manner in good yields, when the reaction was quenched with a soft nucleophile, such as allylsilanes, ketene silyl acetals, and triethylamine. A mechanism involving the initial formation of an episulfonium ion followed by ring-opening by the attack of ArSSAr has been suggested. The reactions of ArS(ArSSAr)⁺ with alkynes also took place to give 1,2-diorganothio-substitued alkenes stereoselectively under similar conditions.     

Catalysis of hydrosilylation of carbon-carbon multiple bonds: Recent progress

Recent progress in the catalytic hydrosilylation of organic and organosilicon compounds containing carbon-carbon multiple bonds is reviewed. Related to this, dehydrogenative silylation is also discussed. During the last decade new hydrosilylation catalysts, predominantly homogenous and heterogenous transition methal complexes, have been developed. These catalysts offer not only increased efficiency and turnover rate but also improved regioselectivity and stereoselectivity; moreover, there has been development in the mechanistic rationale behind these improvements. Application and extension of these basic chemical advances are found in many areas including polyorganosiloxane curing, hydrosilylation polymerization, polysiloxane functionalization, and silicon-containing dendrimer development.     

Metal-metal and carbon-carbon bonds as potential components of molecular batteries

The reductive coupling of [M(salophen)] derivatives, where M is an early transition metal and salophen is N,N'-o-phenylenebis(salicylideneaminato) dianion, led to the formation of dimers linked through C-C and M-M bonds. Both of these bonds can potentially function as electron reservoirs: each bond can be used as a reversible source of a pair of electrons under the condition that it is not chemically transformed by the incoming substrate which functions as an electron acceptor. To explore this potential function as well as the competition in the redox processes between C-C and M-M bonds within the same molecular framework, we investigated the reduction of [(tBu4-salophen)NbCl3] (1) and [(tBu4-salophen)MoCl2] (7) as model compounds. In the former case, the reduction led to [(Nb-Nb)(tBu4-*salophen2*)] (2) which contains both a Nb-Nb bond (2.6528(7) A) and two C-C bonds across two imino groups of the ligand. Complex 2 can be reduced further to a transient compound 5 that contains an Nb=Nb bond. In the second case, the reduction of 7 by two electrons led to [(Mo[triplebond]Mo)(tBu4-salophen)2] (8), which does not contain any C-C linkages between the two salophen units. Complexes 2 and 5 are able to transfer one pair and two pairs of electrons, respectively, to give compounds 3, 4, and 6, with the consequent cleavage of the Nb-Nb and Nb=Nb bonds. In the present case, it is surprising that the C-C bonds do not participate in the reduction of the substrates. A careful theoretical treatment anticipates, both in the case of 1 and 7, the preferential formation of metal-metal bonds upon reduction. This is indeed the case for 7, but not for 1, where the formation of C-C bonds competes with that of M-M bonds, the latter being the first ones, however, to be involved in electron-transfer reactions. The theoretical approach allowed us to investigate the possibility of intramolecular electron transfer from C-C bonds to M-M bonds and vice versa.     

碳碳不饱和键氟化加成反应的研究进展

选择性地向有机物中引入氟原子越来越受到重视，近年来通过碳碳不饱和键的 氟化加成来引入氟原子发展迅速。综述了碳碳不饱和键氟化加成反应的研究进展。     

Reduction of carbon-carbon double bonds and hydrogenolysis by sodium hypophosphite

Sodium hypophosphite plus palladium-charcoal is a mild, economical, selective system for the reduction of carbon-carbon double bonds and hydrogenolysis of benzyl ethers and benzyl carbonates.     

Triosmium-antimony clusters containing the μ,η-phenylene ligand: Unusually long osmium-osmium bonds

The reaction of the osmium-antimony cluster Os₃(μ-H)(μ-SbPh₂)(μ₃,η²-C₆H₄)(CO)₉ with AsPh₃ at room temperature afforded the o-phenylene cluster Os₃(μ-H)(SbPh₂)(μ₂,η²-C₆H₄)(CO)₉(AsPh₃) by nucleophilic addition via a metal-metal bond cleavage, and the substitution product Os₃(μ-H)(SbPh₂)(μ₃,η²-C₆H₄)(CO)₈(AsPh₃). It reacted with ^tBuNC to afford the adduct Os₃(μ-H)(SbPh₂)(μ₂,η²-C₆H₄)(CO)₉(CN^tBu) quantitatively. This adduct isomerised slowly on standing via migration of the isonitrile, while photolysis led to decarbonylation to Os₃(μ-H)(SbPh₂)(μ₂,η²-C₆H₄)(CO)₈(CN^tBu). All the products have been characterised completely, including by X-ray crystallography, and their structures exhibit very long Os-Os bonds.     

Complexes containing indium-gallium bonds

The mixed metal compounds InGaX₄·2L (X = Cl, Br; L = pyridine, piperidine, piperazine, 1,4-dioxan, tetrahydropyran, tetrahydrofuran) have been prepared and also the salts [(n-Bu)₄N]₂ InGaX₆, (X = Cl, Br). Their Raman spectra have been recorded in the solid state and indicate that the compounds contain InGa bonds.     

Biomimetic heterocyclisation of aryl olefins one-step formation of two carbon-carbon bonds

Cyclisation of ethoxylactam 5 in formic acid at room temperature gives rise to stereospecific formation of 9. Similar reaction of the olefin 6 possessing unnatural geometry also proceeds stereospecific and in quantitative yield to the tetracyclic product 10. The acetylene 7 equally affords 11. Upon Me-substitution of the olefinic double bond the cyclisation of 8 has to be carried out in trifluoroacetic acid-dichloromethane in order to obtain a 84% yield of 12 again formed with a high degree of stereoselectivity. The results are discussed on the basis of a mechanism involving synchronous bond formation.     

Catalytic reactions involving the cleavage of carbon-cyano and carbon-carbon triple bonds

The catalytic reactions that involve the cleavage of C-CN bonds and carbon-carbon triple bonds are described in this tutorial review. Regarding the cleavage of a C-CN bond, the catalytic reaction can proceed by two different mechanisms: oxidative addition and deinsertion of silyl isocyanide. A carbon-carbon triple bond can be cleaved in the absence of an organic promoter via the formation of unique organometallic species, such as allenylidene and cyclopropyl carbenoid complexes.