AbstractA highly N2-regioselective functionalization of 2H-1,2,3-triazole and 1H-1,2,3-triazole was achieved via a para-toluenesulfonic-acid-catalyzed olefin hydroamination. The reaction afforded the corresponding products with up to 92 % N2 regioselectivity.

•Efficient way for the synthesis of phosphine oxides and phosphine sulfides from benzyl alcohol derivatives was developed.•Unusual reactivities of Ph2PI were investigated.•A series of pentavalent phosphine compounds have been prepared.•The possible mechanism for the reaction of benzyl alcohol and Ph2PI was proposed.The reaction of benzyl alcohol derivatives with Ph2PI generated in situ from Ph2PCl and NaI provides a facile way to the synthesis of pentavalent phosphine compounds with moderate to excellent yields.Download full-size image

A family of tropos ligands bearing a N-heterocyclic carbene and a chiral oxazoline coordination group with a N-phenyl framework were easily prepared, and their coordination behavior with Pd(II) acetate was performed, affording a series of axially chiral palladium complexes in good yields.A family of tropos ligands bearing a N-heterocyclic carbene and a chiral oxazoline coordination group with a N-phenyl framework were easily prepared, and their coordination behavior with Pd(II) acetate was performed, affording a series of axially chiral palladium complexes in good yields.

A domino palladium-catalyzed hydrogenation reaction was developed to construct 6H-benzo[c]chromene scaffold. Using Pd/C catalyst under H2 balloon, 6H-benzo[c]chromenes were obtained in nearly quantitative yields. However, using Pd(PhCN)2Cl2/DPEphos/AgBF4 as the catalytic system, spiro[benzo[c]chromene-6,2′-chroman]s were obtained in up to 91% yields.

Enantioselective Pd(II)-catalyzed construction of [3.3.1]-bicyclic ketals from 2-hydroxyphenylboronic acid 1 and enone 3 is reported, yielding enantioenriched [3.3.1]-bicyclic ketals in up to 97% yields and 98% ee.

The reaction of aldehydes with Ph2PI provides a facile way to the synthesis of pentavalent phosphine compounds with moderate to good yields.

Me3SiI-promoted reaction of salicylic aldehydes with β-dicarbonyl compounds provided a facile way to construct 4H-benzopyrans in moderate to good yields. This tandem reaction proceeds with high efficiency through nucleophilic addition, silyl enol ether formation, substitution, reduction, and intramolecular nucleophilic cyclization.

Me3SiI-promoted reaction of salicylic aldehydes with ketones via arylmethylation at the α-site of the carbonyl group and cyclodehydration of keto-diol provided a facile way to construct heteroannular ketals, furnishing benzopyranic [2,3-b]ketals and spiroketals in moderate to good yields.

Palladium complexes with an axially chiral N–Ar framework have been developed. These complexes showed high stereoselectivities in asymmetric allylic arylation to achieve the kinetic resolution of Morita–Baylis–Hillman adducts, affording up to 99% ee of (E)-allylation products and 92% ee of recovered Morita–Baylis–Hillman adducts.

Novel dimeric allylpalladium(II) complexes have been successfully synthesized from the transition metal PdCl2-promoted ring-opening reactions of VDCPs 1 in good yields. These dimeric allylpalladium(II) complexes have been characterized by X-ray crystal structure diffraction.

Axially chiral bis(NHC) Pd(II) and Rh(III) complexes with a 1,1′-biphenyl scaffold have been successfully synthesized from the corresponding chiral 6,6′-dimethoxybiphenyl-2,2′-diamine. These interesting NHC-metal complexes have been characterized by X-ray crystal structure diffraction. When applied in the oxidative kinetic resolution of sec-alcohols and hydrosilylation of ketones, these catalysts showed good catalytic activities with moderate to high enantioselectivities.

Me3SiI-promoted reaction of salicylic aldehydes with β-dicarbonyl compounds provided a facile way to construct 4H-benzopyrans in moderate to good yields. This tandem reaction proceeds with high efficiency through nucleophilic addition, silyl enol ether formation, substitution, reduction, and intramolecular nucleophilic cyclization.

Enantioselective Pd(II)-catalyzed construction of [3.3.1]-bicyclic ketals from 2-hydroxyphenylboronic acid 1 and enone 3 is reported, yielding enantioenriched [3.3.1]-bicyclic ketals in up to 97% yields and 98% ee.

Palladium complexes with an axially chiral N–Ar framework have been developed. These complexes showed high stereoselectivities in asymmetric allylic arylation to achieve the kinetic resolution of Morita–Baylis–Hillman adducts, affording up to 99% ee of (E)-allylation products and 92% ee of recovered Morita–Baylis–Hillman adducts.

Me3SiI-promoted reaction of salicylic aldehydes with ketones via arylmethylation at the α-site of the carbonyl group and cyclodehydration of keto-diol provided a facile way to construct heteroannular ketals, furnishing benzopyranic [2,3-b]ketals and spiroketals in moderate to good yields.

The reaction of aldehydes with Ph2PI provides a facile way to the synthesis of pentavalent phosphine compounds with moderate to good yields.