Synthesis of vinyl-substituted alcohols using acetylene as a C2 building block.

Vinyl-substituted alcohols represent a highly useful class of molecular skeletons. The current method typically requires either stoichiometric metallic reagents or preformed precursors. Herein, we report a nickel catalysis-enabled synthesis of vinyl-substituted alcohols a 5-membered oxa-metallacycle.

Correction: Synthesis of vinyl-substituted alcohols using acetylene as a C2 building block.

[This corrects the article DOI: 10.1039/D2SC06400F.].

Palladium-catalyzed intramolecular enantioselective C(sp)-H insertion of donor/donor carbenes.

Herein, the first palladium-catalyzed intramolecular enantioselective C(sp)-H insertion reaction of donor-donor carbenes has been successfully achieved. This facile protocol enables the rapid construction of a collection of enantioenriched decorated indolines with two contiguous stereocenters in a single step. Both enynones and diazo compounds are efficient donor-donor carbene precursors for this reaction.

Cu-catalyzed carboboration of acetylene with Michael acceptors.

A copper-catalyzed three-component carboboration of acetylene with BPin and Michael acceptors is reported. In this reaction, a cheap and abundant C2 chemical feedstock, acetylene, was used as a starting material to afford -alkenyl boronates bearing a homoallylic carbonyl group. The reaction was robust and could be reliably performed on the molar scale.

Rh(ii)-catalyzed enantioselective intramolecular Büchner reaction and aromatic substitution of donor-donor carbenes.

The chiral dirhodium(ii) tetracarboxylate-catalyzed enantioselective intramolecular Büchner reaction of donor/donor-carbenes was reported and a series of valuable chiral polycyclic products were synthesized. Both aryloxy enynones and diazo compounds were efficient carbene precursors for this reaction. Excellent yields (up to 99%) and outstanding enantioselectivities (up to >99% ee) were achieved under standard conditions.

Dirhodium(ii)-catalysed cycloisomerization of azaenyne: rapid assembly of centrally and axially chiral isoindazole frameworks.

Described herein is a dirhodium(ii)-catalyzed asymmetric cycloisomerization reaction of azaenyne through a cap-tether synergistic modulation strategy, which represents the first catalytic asymmetric cycloisomerization of azaenyne. This reaction is highly challenging because of its inherent strong background reaction leading to racemate formation and the high capability of coordination of the nitrogen atom resulting in catalyst deactivation. Varieties of centrally chiral isoindazole derivatives could be prepared in up to 99 : 1 d.