Air oxidative radical hydroxysulfurization of styrenes initiated by 0.5 mol % of tert-butyl hydroperoxide with arylthiols is described, and a new type of difunctionalization of alkenes was achieved.
Functionalization of amines by using CO 2 is of fundamentalimportancec onsidering the abundance of amines and CO 2 .I n this context,t he catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO 2 utilization as aC 1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using ad inuclearM nc omplex in the presenceo fp henylsilane. This robust system also allows for selective formylation and methylation of amines under ar ange of conditions.Catalyticu tilization of CO 2 as aC 1 building block in the functionalization of NÀHb onds is of fundamental importance for developing sustainable chemical transformations. Recent advancesi nt his area have included formylation and methylation, as well as urea/urethane formation, based on innovative usage of organometallic and organocatalysts. [1] Complementary to known formylation reactions, double N-formylation of primary amines providesb is-formylated amine products (N,N-diformylamines),w hich constitutes useful intermediates for drug discovery. [2] N,N-Diformylamine preparation is underdeveloped with scarce reports limited to the use of N,N-diformylacetamide or acetic formic anhydride as the source of formyl group (Scheme 1). However,t hese methods have drawbacks of using harsh conditions and tedious synthetic procedures. [3] Alternatively, double N-formylationo fp rimary amines to N,N-diformylamines has been reported as as ide reactionw hen using CO 2 as carbon source for the reductive formylation of NÀHb onds. Specifically,m ixtures of mono-a nd bis-formylated amines were obtainedi nt he presence of various catalysts, including Zn complexes, [4] N-heterocyclic carbenes, [5] glycineb etaine, [6] g-valerolactone, [7] and metal-organic frameworks. [8] To our knowledge,aselective double N-formylation method is yet to be reported. Hence, the discoveryo fn ovel catalysts to transform abundant CO 2 for this purpose is highly desirable.Herein, we report the first efficient example of selective double N-formylation of primarya rylamines using newly developed dinuclear Mn complexes. The desired N,N-diformylanilines were obtained in good to excellent yields. Furthermore, selectivef ormylation or methylation of amines could be achieved by tuning the reaction parameters. These resultsd emonstrate the important application potential of this methodology for the versatile reductive modification of amines using CO 2 (Scheme 1).In continuation of our interesti nc atalytic utilization of CO 2 , [9] we have undertaken as tudy to develop double N-formylation methods for amine functionalization. For this purpose, double formylation reactions were carried out through in situ catalyst formation by using ligand and metal precursor combination under varioussets of reactionconditions.Initially,w eu sed p-methoxyaniline as am odel substrate and screened various transition metal precursors (Table 1). We observed that the reactivity is clearly affected by the use of different meta...
The trifluoromethylalkynylation of unactivated alkenes with alkynyl sulfones and Togni's reagent was developed. The reaction was catalyzed by 2,4,6-trimethylpyridine, leading to various β-trifluoromethylated alkynes under metal-free conditions with a broad substrate scope and wide functional group compatibility. A mechanism involving catalytic nonchain radical processes is proposed.
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