Straightforward deprotonation of soluble tetramethylammonium salts with alkyllithium reagents gives lithiomethyl trimethylammonium reagents. Coordination of the Li cation is crucial to the stability of these 'N-C ylides'. These reagents were used to prepare epoxides, aziridines and allylic alcohols.

An enantioselective bromoamination of allylic alcohols has been developed for the first time using a newly designed cinchona-derived thiourea as the catalyst and N,N-dibromo-4-nitrobenzenesulfonamide as a bromine and amine source.

Azatitanacyclopropanes (titanaziridines) are shown to be stereochemically labile under reaction conditions for reductive cross-coupling. This fundamental property has been employed to realize highly selective asymmetric coupling reactions with allylic alcohols that proceed by dynamic kinetic resolution.

A direct thionation procedure allows conversion of allylic alcohols into the corresponding thiols, the products of which are immediately compatible with one-pot site-selective selenenyl sulfide mediated protein conjugation.

An enantioselective fluorination of allylic alcohols under chiral anion phase-transfer conditions is reported. The in situ generation of a directing group proved crucial for achieving effective enantiocontrol. In the presence of such a directing group, a range of acyclic substrates underwent fluorination to afford highly enantioenriched α-fluoro homoallylic alcohols. Mechanistic studies suggest...

The photochemistry of tetrazolones derived from the carbocyclic allylic alcohols cyclohex-2-enol and 3-methylcyclohex-2-enol and from the natural terpene alcohol nerol was investigated in solution with the aim of assessing the effect of solvent and of structural constraints imposed by bulky allylic moieties on photoproduct selectivity and stability. Photolysis of tetrazolones derived from nerol...

Here we report the in situ generation of transient allylic boronic species, by reacting TMSCHN2 and E-vinyl boronic acids, followed by their subsequent trapping with aldehydes as electrophiles to yield homoallylic alcohols. This metal-free reaction was initially discovered by the use of a flow chemistry approach to generate a variety of homoallylic alcohols in a straightforward fashion and then...

[reaction: see text] SIBX is a nonexplosive formulation of IBX that can be used as a suspension in a variety of standard organic solvents such as refluxing EtOAc and THF to oxidize safely alcohols into aldehydes and ketones. The use of hot THF is limited to the oxidation of allylic and benzylic alcohols. Most yields are comparable to those obtained with IBX or DMP. SIBX can also be used to perf...

The Pd-catalyzed direct alkylation of H-phosphinic acids and hypophosphorous acid with allylic/benzylic alcohols has been described previously. Here, the extension of this methodology to H-phosphinate esters is presented. The new reaction appears general, although its scope is narrower than with the acids, and its mechanism is likely different. Various alcohols are examined in their reaction wi...

NaBH4 (1.25 equivalents) & NaNO3 (3 equivalents) reduce a variety of aldehydes in the presence of ketones to their corresponding alcohols. Also, regioselectivity and exclusive 1,2reduction enals to their corresponding allylic alcohols in high to excellent yields was achieved successfully with this reducing system. The reduction reactions were carried out in water as green solvent in high to exc...