Design,Synthesis,and Applications of ortho-Sulfur Substituted Arylphosphanes

Ortho-sulfur substituted arylphosphine oxides and arylphosphonates are the precursors of orthosulfurated arylphosphanes,which are widely utilized as ligands in transition metal-catalyzed reactions.However,efficient synthetic methods to access such compounds are sparse.Herein,highly valuable ortho-sulfur substituted arylphosphine oxides and arylphosphonates were constructed via difunctionalization of aryne precursors with P(O)H and elemental sulfur.This method avoids the use of transition metal catalysts and corrosive phosphorus chloride.The synthetic utility of this reaction is further demonstrated by the reduction of the synthesized products to access monophosphine ligands and their applications in cross-coupling reactions.Moreover,by introducing an alkyne moiety into the P(O)H substrate,cyclic sulfur-containing phosphines could be obtained in a one-pot reaction,which represents a new P,S structure that is inaccessible by known strategies.

Synthesis of CF2H-Containing Oxime Ethers Derivatives from CICF2H,tert-Butyl Nitrile and Indoles

Summaryof main observation and conclusion A new and intriguing methodology to access various O-difluoromethylation oxime compounds from CICF2H,TBN and indoles is developed under mild reaction conditions.This strategy can suppress N-difluoromethylation of indoles successfully,in which there are two different active species(:CF2and·NO)while indoles are unprotected,featuringsimple operation and radical involvement.

Deconstrutive Difunctionalizations of Cyclic Ethers Enabled by Difluorocarbene to Access Difluoromethyl Ethers

An unprecedented difluorocarbene-mediated C-O bond cleavage of cyclic ethers for the construction of difluoromethyl ethers is herein disclosed.This protocol is distinguished by its mild conditions,high efficiency,and wide substrate scope,which can tolerate both sensitive functional groups such as the hydroxyl group,olefin and C-C triple bonds,as well as complex molecules.It thus demonstrates excellent chemoselectivities and great potential for late-stage modification of pharmaceutical compounds and natural products.It is worth noting that this method not only introduces fluorine atoms into the final molecules,but it can also effectively form an ester or ether linkage.

Difluorocarbene-enabled access to 1,3-oxazin- 6-ones from enamides

1,3-Oxazin-6-ones as important structural scaffolds widely exist in many bioactive or therapeutic agents.The development of straightforward synthetic approaches to access 1,3-oxazin-6-ones is highly desirable for studying their fundamental properties and applications.