Synthetic exploration of sulfinyl radicals using sulfinyl sulfones
نویسندگان
چکیده
Abstract Sulfinyl radicals – one of the fundamental classes S-centered have eluded synthetic application in organic chemistry for over 60 years, despite their potential to assemble valuable sulfoxide compounds. Here we report successful generation and use sulfinyl a dual radical addition/radical coupling with unsaturated hydrocarbons, where readily-accessed sulfones serve as precursor. The strategy provides an entry variety previously inaccessible linear cyclic disulfurized adducts single step, demonstrates tolerance extensive range hydrocarbons functional groups. Experimental theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl addition.
منابع مشابه
Lithiated sulfoxides: α-sulfinyl functionalized carbanions.
Reactions of alkyl aryl sulfoxides H-CRR'S(O)Ar with n-BuLi-TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine) afforded α-sulfinyl functionalized alkyl aryl lithium compounds of the type [Li2{CRR'S(O)Ar}2(TMEDA)2] (1, R/R' = H/H, Ar = Ph; 2, R/R' = H/H, Ar = p-Tol; 3, R/R' = Me/Me, Ar = Ph; 4, R/R' = H/Ph, Ar = Ph; 5, R/R' = Me/Ph, Ar = Ph). The compounds were characterized by (1)H, (13)C and...
متن کاملGeneration and Decay of Aryl Sulfinyl and Sulfenyl Radicals: A Transient Absorption and Computational Study1
Absorption spectra and extinction coefficients of phenylsulfinyl and phenylsulfenyl (thiyl) radicals are determined by nanosecond laser photolysis in various solvents. Direct observation and characterization of arylsulfinyl radicals from the photolysis of several aromatic sulfoxides provides the strongest evidence to date for R-cleavage as the predominant primary photochemical process for these...
متن کاملRemote regio- and stereocontrol by the sulfinyl group: Diels–Alder reaction of sulfinyl dienols and 8,8-dimethylnaphthalene-1,4,5(8H)-trione
a Facultad de Química y Biología, Departamento de Ciencias del Ambiente, Universidad de Santiago de Chile, Avenida B. O’Higgins 3363, Estación Central, Santiago, CP 9160000, Chile Departamento de Ciencias Químicas, Universidad Andrés Bello, Avenida Concepción, Talcahuano 7100, Concepción, Chile Departamento de Ciencias Químicas, Universidad Andrés Bello, República 237, Santiago, Chile Departame...
متن کاملComputational Investigation of Vicinal Disulfoxides and Other Sulfinyl Radical Dimers
The structure and energetics of the simplest Vic-disulfoxide CH3S(O)S(O)CH3 and its key isomers are reported. Computational methods include a CASSCF[2,2] treatment with a large basis set on sulfur and oxygen, followed by multireference MP2 refinement, and also the hybrid density functional B3LYP. Calculations at the G3 level were also carried out. In contrast to previous reports, a weak bond do...
متن کاملIntra-molecular reactions as a new approach to investigate bio-radical reactivity: a case study of cysteine sulfinyl radicals.
Herein, we demonstrated the use of gas-phase intra-molecular reactions facilitated by collisional activation to investigate bi-molecular reactions with inherent low reactivity. Reactions between sulfinyl radicals (-SO˙) toward free thiol (-SH) were employed as a model system. A new reaction channel, i.e. sulfinyl exchange with thiol, was observed under beam-type collision-induced dissociation (...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Nature Communications
سال: 2021
ISSN: ['2041-1723']
DOI: https://doi.org/10.1038/s41467-021-25593-5