A robust transition-metal-free one-step strategy for the synthesis of ynamides from sulfonamides and (Z)-1,2-dichloroalkenes or alkynyl chlorides is presented. This method is not only effective for internal ynamides but also amenable for terminal ynamides. Various functional groups, even the vinyl moiety, are compatible, and thus, this strategy offers the opportunity for further functionalization.

A convenient and straightforward strategy for the synthesis of 2,3-disubstituted and 2,3,5-trisubstituted furans via a base-promoted domino reaction of β-keto compounds with vinyl dichlorides is described. This transition-metal-free approach proceeds under operationally simple reaction conditions featuring easily available starting materials, a broad substrate scope, and good functional group tolerance.

The first palladium-catalyzed Hiyama crosscoupling of arylsilanes with benzyltrimethylammonium salts is reported. The reaction proceeds smoothly to facilitate C(sp 2 )−C(sp 3 ) bond formation via cleavage of the C−N bond and provides a useful approach to various diarylmethanes with a broad substrate scope and excellent functional group tolerance in good to excellent yields.

A highly efficient palladium-catalyzed Sonogashira coupling of benzylic ammonium salts with terminal alkynes is developed. This strategy provides a facile access to a series of internal alkyne derivatives in moderate to excellent yields via C−N bond cleavage and C(sp 3 )−C(sp) bond formation. The broad substrate scope and high functional group tolerance make this reaction attractive for organic synthesis.A transition-metal-catalyzed coupling reaction has been recognized as a straightforward and powerful tool for constructing carbon−carbon and carbon−heteroatom bonds. 1 Among them, the palladium-catalyzed Sonogashira coupling reaction received considerable attention because this strategy is attractive to organic chemists for the synthesis of internal alkynes with wide applications in materials science, pharmaceutical synthesis, and total synthesis of natural products. 2 These transformations usually employed a variety of electrophiles including aryl iodides, 3 aryl bromides, 4 aryl chlorides, 5 aryl tosylates, 6 aryl triflates, 7 and aryl mesylates 8 as a coupling partner to afford aryl or vinyl internal alkyne derivatives through C(sp 2 )−C(sp) bond formation. In contrast, the construction of the C(sp 3 )−C(sp) bond via the palladiumcatalyzed Sonogashira coupling reaction still remains a challenge due to the competition of β-hydride elimination of the C(sp 3 )−Pd complex formed in situ from the oxidative addition of electrophiles. 9 To realize the formation of the C(sp 3 )−C(sp) bond, in addition to the employment of special

An efficient intermolecular trans-selective β-hydroamidation of ynamides to furnish a series of ( Z)-ethene-1,2-diamide derivatives with excellent regio- and stereo-selectivities is described. The trans-β-addition reactions have been illustrated for a wide range of substrates and proceeded under basic reaction conditions using readily available materials in the absence of a transition-metal catalyst. The synthetic approach to these novel ( Z)-ethene-1,2-diamide derivatives paves the way for further exploration of their synthetic application.