121053-49-4Relevant academic research and scientific papers
The enantioselective chalcogeno-Baylis-Hillman reaction using a chiral hydroxy chalcogenide-TiCl4 complex
Kataoka, Tadashi,Iwama, Tetsuo,Tsujiyama, Shin-Ichiro,Kanematsu, Kiyoko,Iwamura, Tatsunori,Watanabe, Shin-Ichi
, p. 257 - 258 (1999)
The enantioselective chalcogeno-Baylis-Hillman reaction was investigated by the use of chiral hydroxy chalcogenides in the presence of TiCl4 under atmospheric pressure. The best result was obtained with 10-methylthioisobornenol as a chiral hydroxy chalcogenide.
Reactions of PhSCH2Li and NCCH2Li with benzaldehyde and benzophenone: When does the mechanism change from ET to polar?
Yamataka,Sasaki,Kuwatani,Mishima,Shimizu,Tsuno
, p. 2131 - 2135 (2001)
The carbonyl-carbon kinetic isotope effect (KIE) and the substituent effect were measured for the reaction of phenylthiomethyllithium (PhSCH2Li, 1) with benzaldehyde and benzophenone, and cyanomethyllithium (NCCH2Li, 2) with benzaldehyde, and the results were compared with those for other lithium reagents such as MeLi, PhLi, CH2=CHCH2Li, and CH2=C(OLi)C(CH3)3. It was previously shown that the reactions of MeLi, PhLi, and CH2=CHCH2Li proceed via a rate-determining electron transfer (ET) process whereas the reaction of lithium pinacolone enolate goes through the polar (PL) mechanism. The reaction of 1 with benzaldehyde gave no carbonyl-carbon KIE (12k/13k = 0.999 ± 0.004), similar to that measured previously for the MeLi reaction with benzophenone (12k/14k = 1.000). The effect of substituents of the aromatic ring of benzaldehyde and benzophenone on the reactivity gave very small Hammett ρ values of 0.17 ± 0.03 and 0.26 ± 0.05, respectively. These small ρ values are again similar to that observed for the reaction of MeLi. Likewise the reactions of 2 with benzaldehydes gave small KIE and the ρ value (12k/13k = 0.996 ± 0.004, p = 0.14 ± 0.02). Dehalogenation and enone-isomerization probe experiments for 2 showed no evidence for the presence of radical-ion pair of sufficient lifetime during the course of the reaction. It is concluded that the reactions of 1 and 2 with the aromatic carbonyl compounds proceed via the electron transfer-radical coupling mechanism with rate-determining ET as in the reactions of MeLi, PhLi, and CH2=CHCH2Li.
Solvent-mediated switching between oxidative addition and addition-oxidation: Access to β-hydroxysulfides and β-arylsulfones by the addition of thiols to olefins in the presence of Oxone
Moorthy, Jarugu Narasimha,Payra, Soumen,Yadav, Navin
, p. 582 - 591 (2022/01/22)
The reaction between aryl olefins and thiols in the presence of Oxone in toluene-water (9:1, v/v) affords β-hydroxy-2-arylethyl aryl sulfides smoothly by the interception of intermediary thiyl radicals with aryl olefins; the former are generated by the ox
PhB(OH)2-Promoted Electrochemical Sulfuration-Formyloxylation of Styrenes and Selectfluor-Mediated Oxidation-Olefination
Zhao, Yulei,Guo, Xuqiang,Li, Shuai,Fan, Yuhang,Sun, Xuejun,Tian, Laijin
supporting information, p. 9140 - 9145 (2021/11/30)
We report a PhB(OH)2-promoted electrochemical sulfuration-formyloxylation reaction of styrenes employing commercially available thiophenols/thiols as thiolating agents. Specifically, metal catalysts and external chemical oxidants are not needed in the reaction for the formation of β-formyloxy sulfides, and these sulfides can be further converted to (E)-vinyl sulfones via the Selectfluor-mediated oxidation-olefination. Notably, on the basis of this electrochemical oxidation strategy, β-hydroxy sulfide, β-formyloxy sulfoxide, β-formyloxy sulfone, and (E)-vinyl sulfoxide can also be easily prepared.
Synthesis and application of Cu(II) immobilized MCM-41 based solid Lewis acid catalyst for aminolysis reaction under solvent-free condition
Chaudhary, Garima,Gupta, Neha,Singh, Amit Pratap
supporting information, (2021/07/22)
In this paper, a Cu(II) immobilized periodic mesoporous organosilica (PMOs) was synthesized and used as a reusable solid Lewis acid catalyst for the aminolysis of epoxides under solvent-free conditions. An amide-based ligand, L-propylsilyl (1) having a specific binding pocket was prepared and fabricated on mesoporous MCM-41 to produce mesoporous organosilica L-propylsilyl@MCM-41 (2). Further, it has been utilized for anchoring Cu(II) ions under controlled reaction conditions to yield solid Lewis acid catalyst Cu(II)-L-propylsilyl@MCM-41 (3). The synthesized catalyst 3 exhibits significantly higher catalytic activity for aminolysis compared to hitherto known solid Lewis acid catalysts. An extensive range of β-amino alcohols with high regio and stereoselectivity were prepared by using catalyst 3. The catalyst was recovered easily and reused eight times without any loss in its catalytic activity. Furthermore, the synthesis of clinically significant propranolol (β-blocker) from α- naphthyl glycidyl ether was attained successfully using catalyst 3 in a very decent yield.
Competition Between Cα-S and Cα-Cβ Bond Cleavage in β-Hydroxysulfoxides Cation Radicals Generated by Photoinduced Electron Transfer?
Lapi, Andrea,D'Alfonso, Claudio,Del Giacco, Tiziana,Lanzalunga, Osvaldo
, p. 1310 - 1321 (2021/06/07)
A kinetic and product study of the 3-cyano-N-methyl-quinolinium photoinduced monoelectronic oxidation of a series of β-hydroxysulfoxides has been carried out to investigate the competition between Cα-S and Cα-Cβ bond cleavage within the corresponding cation radicals. Laser flash photolysis experiments unequivocally established the formation of sulfoxide cation radicals showing their absorption band (λmax ≈ 520?nm) and that of 3-CN-NMQ? (λmax ≈ 390?nm). Steady-state photolysis experiments suggest that, in contrast to what previously observed for alkyl phenyl sulfoxide cation radicals that exclusively undergo Cα-S bond cleavage, the presence of a β-hydroxy group makes, in some cases, the Cα-Cβ scission competitive. The factors governing this competition seem to depend on the relative stability of the fragments formed from the two bond scissions. Substitution of the β-OH group with -OMe did not dramatically change the reactivity pattern of the cation radicals thus suggesting that the observed favorable effect of the hydroxy group on the Cα-Cβ bond cleavage mainly resides on its capability to stabilize the carbocation formed upon this scission.
Air-Induced Disulfenylation of Alkenes: Facile Synthesis of Vicinal Dithioethers
Chen, Danyao,Chen, Qian,Huang, Yuanting,Ou, Yingcong,Yan, Y.,Yu, Guodian
, p. 83 - 86 (2019/12/30)
A novel disulfenylation of alkenes with thiophenols and their corresponding disulfides by using air as the oxidant has been achieved. This transformation provides a facile and practical protocol for the synthesis of vicinal dithioethers under mild conditions.
Gem-Heterosubstituted (stannyl)methylsilanes as synthetic equivalents of functionalized α-stannyl(methyl) anions
Tanini, Damiano,Nocentini, Tiziano,Capperucci, Antonella
, p. 99 - 113 (2020/02/13)
α-Heterosubstituted silyl derivatives, such as phenylthio-, phenylseleno- and benzotriazolyl-stannyl silanes, react with aldehydes under tetra-n-butylammonium fluoride (TBAF) catalysis, leading to α-substituted-βhydroxy stannanes, able to behave as precursors of Z- and E-olefins, generated by deoxystannylation. This reactivity shows the capability of such heterosubstituted silanes to act as masked carbanions through a mild functionalization of the carbon-silicon bond.
Aerial dioxygen activation: Vs. thiol-ene click reaction within a system
Choudhuri, Khokan,Mandal, Arkalekha,Mal, Prasenjit
supporting information, p. 3759 - 3762 (2018/04/16)
Markovnikov or anti-Markovnikov selective thiol-ene click (TEC) reactions and the synthesis of β-hydroxysulfides via aerial dioxygen activation are prevalent C-S bond forming reactions of styrenes and thiophenols. Herein, by choosing appropriate environme
Enantioselective, Lewis Base-Catalyzed Carbosulfenylation of Alkenylboronates by 1,2-Boronate Migration
Tao, Zhonglin,Robb, Kevin A.,Panger, Jesse L.,Denmark, Scott E.
supporting information, p. 15621 - 15625 (2018/11/23)
A catalytic, enantioselective method for the preparation of chiral, non-racemic, alkylboronic esters bearing two vicinal stereogenic centers is described. The reaction proceeds via a 1,2-migration of a zwitterionic thiiranium-boronate complex to give excl
