116233-90-0Relevant articles and documents
Continuous Flow Synthesis of 2H-Thiopyrans via thia-Diels–Alder Reactions of Photochemically Generated Thioaldehydes
Sachse, Florian,Gebauer, Konrad,Schneider, Christoph
supporting information, p. 64 - 71 (2020/11/30)
Herein, we report a novel protocol for the photochemical generation of thioaldehydes in a continuous flow process which were in situ reacted with electron rich 1,3-butadienes in thia-Diels–Alder reactions. A broad range of 3,6-dihydro-2H-thiopyrans were formed as products in much higher yields and productivities as compared to classical batch processes. Moreover, greatly reduced reaction times and a facile large-scale preparation of products were achieved by fully exploiting the advantages of continuous flow technology.
Protiodesilylation of 3-trimethylsilyl-2-thiabicyclo[2.2.1]hept-5-enes and derivatives: A stereochemical study
Bonini, Bianca F.,Masi, Enza,Masiero, Stefano,Mazzanti, Germana,Zani, Paolo
, p. 3553 - 3562 (2007/10/03)
endo- and exo-trimethylsilyl-3-phenyl-2-thiabicyclo[2.2.1]hept-5-enes, the endo-trimethylsilyl-exo-S-oxide and their S,S-dioxide derivatives were protiodesilylated with fluoride ion. Stereoconvergent reactions were found, affording the endo-phenyl derivatives. These results can be rationalised with the hypothesis of a common carbanionic intermediate. In contrast, the desilylation of 3-endo-trimethylsilyl-3-exo-phenyl-2-thiabicyclo[2.2.1]heptane gave a mixture of endo- and exo-isomers, thus proving the involvement of the double bond in the control of the reaction stereoselectivity.
STEREOCHEMISTRY OF PROTIODESILYLATION OF 3-TRIMETHYLSILYL-2-THIABICYCLOHEPTENES, HEPTANES AND DERIVATIVES.
Bonini, Bianca Flavia,Masi, Enza,Masiero, Stefano,Mazzanti, Germana,Zani, Paolo
, p. 379 - 380 (2007/10/02)
Some 3-trimethylsilyl-2-thiabicycloheptenes and heptanes of known configuration were protiodesilylated and the stereochemistry of the reaction was studied.Evidences for a carbanionic intermediate as well as the pivotal role played by the metal coun
Formation of Thiocarbonyl Compounds in the Reaction of Ebselen Oxide with Thiols
Glass, Richard S.,Farooqui, Firdous,Sabahi, Mahmood,Ehler, Kenneth W.
, p. 1092 - 1097 (2007/10/02)
Reaction of α-toluenethiol with Ebselen oxide, 2, affords dibenzyl disulfide and seleno sulfide 5, R = PhCH2.In the course of this reaction, thiobenzaldehyde is formed and can be trapped with cyclopentadiene in 90percent yield.Reaction of 2-propene-1-thiol with 2 afforded thioacrolein dimer in 69percent yield and seleno sulfide 5, R = CH2-CH=CH2.Trapping, stereochemical, and isotopic exchange studies were used to determine if in the reaction of 2 with 1-heptanethiol, cyclohexanethiol, and N-acetyl-D,L-cysteine thiocarbonyl compounds heptanethial, cyclohexanethione, and 2-acetamino-3-thioxopropanoic acid (α-thioformyl-N-acetylglycine), respectively, are also formed.These studies showed that free thiocarbonyl compounds are not formed in these reactions.
Diastereoselectivity in the Diels-Alder Reactions of Thioaldehydes
Vedejs, E.,Stults, J. S.,Wilde, R. G.
, p. 5452 - 5460 (2007/10/02)
The Diels-Alder reaction of thioaldehydes with cyclopentadiene occurs with a preference for the endo isomer.The highest selectivity is observed for thioaldehydes RCHS where R is a bulky group such as tert-butyl or isopropyl.Thioaldehydes having α-alkoxy, acetoxy, or siloxy substituents also react with useful endo selectivity.Secondary orbital overlap is a small factor in these reactions since α-oxo thioaldehydes react with relatively low endo selectivity.Steric effects are primarily responsible for the endo preferences observed.The Diels-Alder reactions of chiral α-oxygen substituted thioaldehydes also occur with useful thioformyl face selectivity.A Cornforth transition state 5 is most likely for the selectivity observed for α-alkoxy or acetoxy thioaldehydes, but the α-hydroxy analogue 23 reacts with the opposite facial preference.The highest face selectivity is obtained with the acetonide of thioglyceraldehyde, generated by photolysis of the phenacyl sulfide 15b.
Thioaldehyde Diels-Alder Reactions
Vedejs, E.,Eberlein, T. H.,Mazur, D. J.,McClure, C. K.,Perry, D. A.,et al.
, p. 1556 - 1562 (2007/10/02)
Thioaldehydes containing virtually any α-substitutent can be generated by photofragmentation of phenacyl sulfides.Donor-substituted derivatives are reactive toward electron-rich dienes and give 2 + 4 cycloadducts with regiochemistry corresponding to advan
GENERATION OF THIOALDEHYDES VIA FLUORIDE INDUCED ELIMINATION OF Α-SILYLDISULFIDES
Krafft, Grant A.,Meinke, Peter T.
, p. 1947 - 1950 (2007/10/02)
A mild, efficient and general method for the generation of reactive thioaldehydes from α-silyldisulfides is described.
Transformation of Thiosulphonates into α-Sulphonyldisulphides, a New Class of Thioaldehyde Precursors
Kirby, Gordon W.,Lochead, Alistair W.,Sheldrake, Gary N.
, p. 1469 - 1470 (2007/10/02)
Toluene-p-thiosulphonates, RCH2SSO2Tol (1) where R is an electron-withdrawing group, are transformed readily into α-sulphonyldisulphides (2) which, with triethylamine, undergo fragmentation-elimination to give 2 moles of thioaldehydes, RCHS.
