Compaction matters: SN2 substitution represents an important class of reaction for both chemical and biological systems. The ability to assess enzymatic transition state structure within this class of reaction remains a major experimental challenge. Here, we comment on and compare the relative impact of compaction along the axis of reaction to the impact of an orthogonal CH···O hydrogen bonding...

The synthesis of a novel class of hexa-arm molecules with C(3d) symmetry via a simultaneous six-fold nucleophilic substitution reaction from 1,4,5,8,9,12-hexabromododecahydrotriphenylene has been described.

The reaction of ketone 1 with primary organolithium reagents in THF/HMPA affords not the expected carbonyl addition product but the product of bromide substitution, in reasonable yield.

Despite recent advances, trifluoromethoxylation remains a challenging reaction. Here we describe an efficient trifluoromethoxylative substitution, using inexpensive and easy-to-handle reagent. By mixing DMAP with slight excess of 1,4-dinitro-trifluoromethoxybenzene (DNTFB), stable solution trifluoromethoxide anion is obtained can be used to perform SN2 reaction without any silver additives. A p...

substitution product, Tp(PPh3)(CH3CN)RuCdC(Ph)CHCN (4). The cyclopropenyl ring in 3 and 4 is susceptible to ring opening by electrophiles such as CF3COOH, Ph3CPF6, and HgCl2. The substitution reaction of 3 with pyrazole is followed by an intramolecular nucleophilic addition of the nitrogen atom at the R-carbon atom to afford the metallacyclic complex, Tp(PPh3)Ru(C3H3NN)CdC(Ph)CH2CN (8a). The re...

A catalytic method has been developed for the determination of microgram amounts of mercury (II) based on its catalytic effect on the rate of a ligand substitution reaction. The reaction studied involved the substitution of cyanide in hexacyanoferrate (II) by resacetophenone benzoic acid hydrazone (2’, 4’dihydroxy propiophenone benzoic acid hydrazone) and the reaction was monitored spectrophoto...

The substitution of a siloxy group using thiosilanes smoothly occurred in the presence of InI₃ catalyst to yield the corresponding thioethers. InI₃ was a specifically effective catalyst in this reaction system, while other typical Lewis acids such as BF₃⋅OEt₂, AlCl₃, and TiCl4 were ineffective. Various silyl ethers such as primary alkyl, secondary alkyl, tertiary alkyl, allylic, benzylic, and p...