82352-39-4Relevant academic research and scientific papers
Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Br?nsted acids. NMR and DFT study of these cations and their reactions
Lozovskiy, Stanislav V.,Ivanov, Alexander Yu.,Khoroshilova, Olesya V.,Vasilyev, Aleksander V.
, p. 2897 - 2906 (2018/12/13)
In strong Br?nsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2-CR1=C-C(Me)=CH2, for R2 = R3 = Me, yields of 87-98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)-HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3, yields of 78-99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-diox-ides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.
Rhodium-Catalyzed Highly Regio- and Enantioselective Hydrogenation of Tetrasubstituted Allenyl Sulfones: An Efficient Access to Chiral Allylic Sulfones
Long, Jiao,Shi, Liyang,Li, Xiong,Lv, Hui,Zhang, Xumu
, p. 13248 - 13251 (2018/09/21)
A highly regio- and enantioselective hydrogenation of challenging tetrasubstituted allenyl sulfones has been developed, affording chiral allylic sulfones in good yields with excellent regio- and enantioselectivities (up to 99 % yield and 99 % ee). This me
Preparation of Propargylic Sulfinates and their [2,3]-Sigmatropic Rearrangement to Allenic Sulfones
Tata, Rama Rao,Hampton, Carissa S.,Harmata, Michael
, p. 1232 - 1241 (2017/04/11)
The scope of the [2,3]-sigmatropic rearrangement of propargylic sulfinates to allenic sulfones by silver catalysis was expanded. A series of new propargylic sulfinate esters was generated from a variety of aromatic and heteroaromatic sulfonyl chlorides an
[2,3] sigmatropic rearrangement of propargylic sulfinates by a pale Ag1-USY zeolite and silver salts
Hamptona, Carissa S.,Harmata, Michael
supporting information, p. 549 - 552 (2015/02/19)
The sigmatropic rearrangement of propargylic sulfinates to allenic sulfones is catalyzed by the silver cation. The Ag1-USY zeolite, as well as non-coordinating silver salts, lead to essentially quantitative yields of the corresponding allenic s
Silver-catalyzed rearrangement of propargylic sulfinates to allenic sulfones
Harmataa, Michael,Huanga, Chaofeng
experimental part, p. 972 - 974 (2009/05/27)
Treatment of propargylic sulfinate esters with 2 mol% of silver hexafluoroantimonate results in the rapid formation of allenic sulfones in essentially quantitative yield.
Synthesis of thiophenes from allenyl sulfones involving α,β-unsaturated sulfines as intermediates
Linden, Johannes B. van der,Asten, Peter F. T. M. van,Braverman, Samuel,Zwanenburg, Binne
, p. 51 - 60 (2007/10/02)
The synthesis of thiophenes starting from allenyl sulfones, via intermediate formation of α,β-unsaturated sulfines, is described.The allenyl sulfones were synthesized by a -sigmatropic rearrangement of appropriately substituted prop-2-ynyl sulfinates
Studies on the Addition of Allyl Oxides to Sulfonylallenes. Preparation of Highly Substituted Allyl Vinyl Ethers for Carbanionic Claisen Rearrangements
Denmark, Scott E.,Harmata, Michael A.,White, Kathleen S.
, p. 4031 - 4042 (2007/10/02)
Thirty-five allyl vinyl ethers bearing an arylsulfonyl anion-stabilizing group have been prepared by addition of allylic alkoxides to (arylsulfonyl)allenes.The allyl vinyl ethers are produced as either β,γ-unsaturated or α,β-unsaturated sulfones depending upon the substitution pattern of the allene and the reaction conditions.A wide variety of substitution patterns are available by using this method.Factors that control the position and stereochemistry of the vinyl ether double bond are discussed.
CARBANION-ACCELERATED CLAISEN REARRANGEMENTS 3. VICINAL QUATERNARY CENTERS
Denmark, Scott E.,Harmata, Michael A.
, p. 1543 - 1546 (2007/10/02)
The preparation and Claisen rearrangement of highly substituated allyl vinyl ethers is described.It is demonstrated that the thermal and anionic versions of the Claisen rearrangement are capable of creating vicinal quaternary centers.
