Synthesis of heteroatom-containing ladder-type π-conjugated molecules was successfully achieved via a palladium-catalyzed intramolecular oxidative C-H/C-H cross-coupling reaction. This reaction provides a variety of π-conjugated molecules bearing heteroatoms, such as nitrogen, oxygen, phosphorus, and sulfur atoms, and a carbonyl group. The π-conjugated molecules were synthesized efficiently, even in gram scale, and larger π-conjugated molecules were also obtained by a double C-H/C-H cross-coupling reaction and successive oxidative cycloaromatization.

A catalytic enantioselective method for the synthesis of 2-(2-hydroxyethyl)indole scaffolds was developed.The process includes catalytic intramolecular amido-cupration of an allene to generate a novel allylcopper species, followed by asymmetric addition of the thus-generated chiral nucleophile to aldehydes and ketones. This is the first example of catalytic indole formation coupled with asymmetric C-C bond formation via in situ generation of a reactive chiral allylcopper species.

Asymmetric allylation of carbonyl groups has been extensively studied because of the high versatility of enantiomerically enriched homoallylic alcohols. [1] There are four main methods for catalytic asymmetric carbonyl allylation: a) using allylmetal species (such as allyl tin, allyl silicon, and allyl boron reagents), [2] b) using the catalytic variant of the Nozaki-Hiyama reaction, [3] c) using reductive generation of nucleophilic p-allyl palladium from allylic alcohols or acetates, [4] and d) using catalytic transfer hydrogenation [5] of various precursors, such as allyl acetates, [6] allenes, [7] and dienes [8] in a waste-minimal manner. Those methods are reliable and widely used in organic synthesis. In contrast, despite potential utility, in situ generation of nucleophilic allylmetal species by oxymetallation has been less explored.Herein we report the sequential intramolecular oxycupration of allenes [9][10][11] and subsequent asymmetric addition of the in situ generated allylcopper intermediates to carbonyl compounds (Figure 1). [12] This method has four characteristic

We describe the development of an intermolecular unactivated C(sp3)–H bond functionalization towards the direct synthesis of tertiary carbamates.

The transition-metal-free economical solid phase synthesis of 1,2-disubstituted 4-quinolones has been developed via the novel regiospecific synthesis of enaminones.