107270-96-2Relevant academic research and scientific papers
Photocatalyzed site-selective C(sp3)-H sulfonylation of toluene derivatives and cycloalkanes with inorganic sulfinates
Cao, Shi,Gong, Lei,Lin, Yu-Mei,Lu, Cheng,Sha, Liyuan,Zhang, Shaonan
, p. 564 - 570 (2022/02/05)
The development of practical methods for the direct and selective C(sp3)-H functionalization of hydrocarbons is an attractive topic in synthetic chemistry. Although the radical-mediated hydrogen atom transfer (HAT) process has shown considerable potential in such reactions, it still faces fundamental problems associated with reactivity and selectivity. Herein, we report a convenient and economic approach to site-selective C(sp3)-H sulfonylation via photo-induced HAT catalysis. Employing a conjugated polycyclic quinone as a direct HAT photocatalyst, commercially available inorganic sulfinates as the sulfonylation source, copper triflate as an inexpensive oxidant, a variety of toluene derivatives and cycloalkanes were converted into biologically and synthetically interesting sulfone products under mild conditions. The mechanistic studies reveal that the reaction sequence involves direct HAT-induced radical formation and a subsequent copper-mediated organometallic process for the C-S bond formation. This method offers an appealing opportunity to furnish high value-added products from abundant hydrocarbon starting materials and inexpensive reagents.
Catalyst-free alkylation of sulfinic acids with sulfonamides via sp 3 C-N bond cleavage at room temperature
Liu, Cong-Rong,Li, Man-Bo,Cheng, Dao-Juan,Yang, Cui-Feng,Tian, Shi-Kai
supporting information; experimental part, p. 2543 - 2545 (2009/10/10)
An unprecedented catalyst-free alkylation of sulfinic acids with sulfonamides has been developed via sp3 C-N bond cleavage at room temperature. In the absence of external catalysts and additives, a wide variety of N-benzylic and N-allylic sulfonamides couple with sulfinic acids to give structurally diversified sulfones in moderate to excellent yields. Furthermore, the reaction of N-(2-acyl)allylic sulfonamides with sulfinic acids provides a convenient access to trisubstituted allyl sulfones with exclusive Z selectivity.
An expeditious entry to benzylic and allylic sulfones through byproduct-catalyzed reaction of alcohols with sulfinyl chlorides
Li, Hai-Hua,Dong, De-Jun,Jin, Yin-Huan,Tian, Shi-Kai
supporting information; experimental part, p. 9501 - 9504 (2010/03/04)
(Chemical Equation Presented) In the absence of external catalysts and additives, a broad range of benzylic and allylic alcohols react with various sulfinyl chlorides to afford structurally diversified benzylic and allylic sulfones in moderate to excellen
Solvolytic Generation of α-Sulfonyl and α-Sulfinyl Carbocations
Creary, Xavier,Mehrsheikh-Mohammadi, M.E.,Eggers, Mark D.
, p. 2435 - 2442 (2007/10/02)
A series of mesylates of general type ArC(CH3)(SO2Ph)OMs, 14, have been prepared and studied under solvolytic conditions.The Hammett p value in methanol is -7.98.A solvent effect study on 14b, where Ar=p-CH3C6H4, gave a good correlation with YOTs values and an m value of 0.85.These data were interpreted in terms of the involvement of α-sulfonyl-substituted carbocations, which have a large demand for aryl group stabilization.In solvolyses of 14b, capture of the α-sulfonyl carbocation by acetic or trifluoroacetic acid gave simple substitution products which could be isolated.In alcohol solvents subsequent unimolecular loss of benzenesulfinate ion from the initially formed α-alkoxy sulfone led ultimately to the formation of ketones or ketals.Analogous loss of benzenesulfinate from the primary product is also seen on prolonged reaction of 14b in carboxylic acid solvents.Solvolyses of a series of α-bromo sulfoxides of general structure ArC(CH3)(SOPh)Br, 35, also proceed via the intermediacy of carbocations.The demand for aryl stabilization in these α-sulfinyl cations is also quite large as evidenced by the p value of -7.18 in trifluoroethanol.The trifluoroethanolysis rate of 35b, where Ar=p-CH3C6H4, is 1.4x105 times slower at 25 deg C than that of the α-H analogue ArCH(CH3)Br, 29.This, along with the large negative p value, implies that the interaction of the sulfur nonbonding electrons with the adjacent cationic center is of minimal importance in the α-sulfinyl carbocation derived from 35b.These data conflict with previous suggestion that α-sulfinyl cations are greatly stabilized by the sulfur nonbonding electrons.Suggestions are offered to explain this apparent conflict.The relative reactivities of a series of bromides containing electron-withdrawing groups have been determined in the common solvent trifluoroethanol in order to evaluate the effect of these groups on the rate of carbocation generation.The relative reactivity order for sovolyses of substrates of general type p-CH3C6H4C(CH3)BrE, where E is an electronegative group, is COPh>PO(OEt)2>CN>SOPh>CF3>SO2Ph.
