Dehydrative alkynylation of 3-hydroxyisoindolinones with terminal alkynes for the synthesis of 3-alkynylated 3,3-disubstituted isoindolinones.

A brand-new procedure for the synthesis of 3-alkynylated 3,3-disubstituted isoindolinones has been disclosed via a HOTf or Fe(OTf)3-catalyzed dehydrative alkynylation of 3-hydroxyisoindolinones with terminal alkynes. Aryl, alkenyl and alkyl terminal alkynes are suitable to couple with a broad range of 3-hydroxyisoindolinones to afford the desired products in moderate to good yields. This protocol features the use of an inexpensive catalyst, mild reaction conditions, broad substrate scope and easy elaboration of the products.

Tandem phospha-Michael addition/cyclization/dehydration of 2-hydroxychalcones with H-phosphine oxides for the synthesis of 4-phosphorylated 4H-chromenes.

A Hg(OTf)2-catalyzed tandem phospha-Michael addition/cyclization/dehydration of 2-hydroxychalcones with H-phosphine oxides is presented. This protocol provides a new and supplementary approach for the preparation of 4-phosphorylated 4H-chromenes in good yields (up to 99%). In addition, this domino reaction allows the successful construction of two new C-P and C-O bonds in a one-pot operation.

Copper(II)-catalyzed direct dehydrative alkynylation of 2H-chromene hemiketals with terminal alkynes to 2,2-disubstituted 2-alkynylated 2H-chromenes.

The first copper-catalyzed direct dehydrative alkynylation of 2H-chromene hemiketals with terminal alkynes has been uncovered. The use of cheap and readily available CuCl2 as the catalyst allowed the preparation of various 2,2-disubstituted 2-alkynylated 2H-chromenes in moderate to good yields, which compensates for the limitation of the current methods only suited for the synthesis of 2-monosubsituted 2-alkynylated 2H-chromenes.

Synthesis of 2H-chromenes: recent advances and perspectives.

As one type of chromene, 2H-chromenes represent important oxygen heterocycles, which not only widely exist in natural products, pharmaceutical agents and biologically relevant molecules, but have also been used broadly in materials science and organic synthesis. Two major synthetic strategies have been developed towards such compounds. This review mainly focuses on the recent advances in this field, including benzopyran ring formation involving cyclization reactions and the late-stage functionalization of the parent 2H-chromenes.

Y(OTf)3-catalyzed phosphorylation of 2H-chromene hemiacetals with P(O)-H compounds to 2-phosphorylated 2H-chromenes.

A facile synthesis of 2-phosphorylated 2H-chromenes has been accomplished herein via a Y(OTf)3-catalyzed dehydrative coupling of 2H-chromene hemiacetals with P(O)-H compounds. This protocol features low catalyst loading, mild reaction conditions, broad substrate scope and easy elaboration of the products.