A photocatalytic process for selective arylalkylation of allylic alcohols with α-bromo diethyl malonate has been developed. The reaction provided a straightforward approach to synthesize α-aryl-β-alkylated ketones via unique 1,2-aryl migration. The procedure is highlighted by its operational simplicity and mild reaction conditions.

The first metal-free reduction of lignin model compounds is described. Using inexpensive Et3SiH, PMHS and TMDS hydrosilanes as reductants, α-O-4 and β-O-4 linkages are reduced to primary alcohols and phenols under mild conditions using B(C6F5)3 as an efficient catalyst.

A practical and efficient palladium-catalyzed direct allylation of β-dicarbonyl compounds with both cyclic and acyclic Morita-Baylis-Hillman (MBH) alcohols, using Et3B as a Lewis acid promoter, is described herein. A wide range of the corresponding functionalized allylated derivatives have been obtained in good yields and with high selectivity.

The title compound, C(11)H(15)BrNO(+)·Cl(-), was obtained as a precursor within our current program for the synthesis of new β-amino-alcohols via a Mannich-type reaction. The protonated amino N atom is hydrogen bonded to the chloride anion. With exception of one methyl group, the cation is approximately planar (r.m.s. deviation for all non H-atoms = 0.069 Å).

Efficient asymmetric bio-epoxidation of electron-deficient α,β-unsaturated ketones was realized via a tandem reduction-epoxidation-dehydrogenation cascade, which proceeds in a switchable manner to afford either chiral epoxy ketones or allylic epoxy alcohols with up to >99% yield and >99%ee.

A copper-catalyzed cross-coupling reaction of epoxides with arylboronates is described. This reaction is not limited to aromatic epoxides, because aliphatic epoxides are also suitable substrates. In addition, N-sulfonyl aziridines can be successfully converted into the products. This reaction provides convenient access to β-phenethyl alcohols, which are valuable synthetic intermediates.

Synthesis of β-C-D-galactosyl D- and L-alanines is carried out via a highly stereoselective Grignard reaction of glycosyl iodides, Sharpless dihydroxylation and S(N)2 displacement of the corresponding mesylate or tosylate. Alternatively, attempted triflation of the intermediate alcohols triggers a stereoselective debenzylative cyclization leading to interesting bicyclic trans-fused compounds.

Novel, efficient and mild preparation of 7- and 8-membered cyclic di- and 10-membered cyclic tripeptides containing α-, β- or γ-amino acid residues is effected by a Staudinger-mediated ring closure. Medium-sized cyclic di- and tripeptides--recognized as difficult targets--were obtained in moderate to good yields according to a straightforward sequence. Empirical force-field calculations were un...

IBX facilitated the reaction of β-enamino esters with allylic alcohols affording a direct, one-pot and metal free synthesis of functionalized pyridines including 2-substituted nicotinic acids, densely substituted pyridines and precursors of azafluorenones. The methodology also afforded the racemic pyridine core of cyclothiazomycin.

Carbonyl rhenium(I) complexes are efficient catalysts for the regioselective isomerization of terminal propargylic alcohols into α,β-unsaturated aldehydes or ketones which can be used as an unprecedented recyclable catalytic system (up to 10 consecutive runs) in the ionic liquid [BMIM][PF(6)].