111832-37-2Relevant articles and documents
Primary Alcohols via Nickel Pentacarboxycyclopentadienyl Diamide Catalyzed Hydrosilylation of Terminal Epoxides
Lambert, Tristan H.,Steiniger, Keri A.
supporting information, p. 8013 - 8017 (2021/10/25)
The efficient and regioselective hydrosilylation of epoxides co-catalyzed by a pentacarboxycyclopentadienyl (PCCP) diamide nickel complex and Lewis acid is reported. This method allows for the reductive opening of terminal, monosubstituted epoxides to form unbranched, primary alcohols. A range of substrates including both terminal and nonterminal epoxides are shown to work, and a mechanistic rationale is provided. This work represents the first use of a PCCP derivative as a ligand for transition-metal catalysis.
Design, Synthesis, and Evaluation of 2-(arylsulfonyl)oxiranes as Cell-permeable Covalent Inhibitors of Protein Tyrosine Phosphatases
Dana, Dibyendu,Das, Tirtha K.,Kumar, Ish,Davalos, Anibal R.,Mark, Kevin J.,Ramai, Daryl,Chang, Emmanuel J.,Talele, Tanaji T.,Kumar, Sanjai
, p. 489 - 499 (2012/11/06)
A structure-based design approach has been applied to develop 2-(arylsulfonyl)oxiranes as potential covalent inhibitors of protein tyrosine phosphatases. A detailed kinetic analysis of inactivation by these covalent inhibitors reveals that this class of compounds inhibits a panel of protein tyrosine phosphatases in a time- and dose-dependent manner, consistent with the covalent modification of the enzyme active site. An inactivation experiment in the presence of sodium arsenate, a known competitive inhibitor of protein tyrosine phosphatase, indicated that these inhibitors were active site bound. This finding is consistent with the mass spectrometric analysis of the covalently modified protein tyrosine phosphatase enzyme. Additional experiments indicated that these compounds remained inert toward other classes of arylphosphate-hydrolyzing enzymes, and alkaline and acid phosphatases. Cell-based experiments with human A549 lung cancer cell lines indicated that 2-(phenylsulfonyl)oxirane (1) caused an increase in intracellular pTyr levels in a dose-dependent manner thereby suggesting its cell-permeable nature. Taken together, the newly identified 2-(arylsulfonyl)oxiranyl moiety could serve as a novel chemotype for the development of activity-based probes and therapeutic agents against protein tyrosine phosphatase superfamily of enzymes.
A new synthesis of β-keto phosphonate from aryl epoxysulfones and dialkyl hydrogen phosphite
Koh, Young Joo,Oh, Dong Yung
, p. 2147 - 2148 (2007/10/02)
Reaction of α-subtituted arylsulfonyl epoxide with diethyl phosphite sodium salt gave β-keto phosphonate in good yield.
PREPARATION AND RING-OPENING REACTIONS OF 2-PHENYLSULPHONYL-2-TRIMETHYLSILYL OXIRANES
Hewkin, Cheryl T.,Jackson, Richard F. W.
, p. 1877 - 1880 (2007/10/02)
Reaction of 2-phenylsulphonyl oxiranes (1) with butyllithium in the presence of chlorotrimethylsilane gave 2-phenylsulphonyl-2-trimethylsilyl oxiranes (2), which on treatment with MgBr2*Et2O gave 2-bromoacylsilanes (3) and either bromovinyl sulphones (5)
A stereocontrolled approach to electrophilic epoxides
Meth-Cohn, Otto,Moore, Clive,Taljaard, Heinrich C.
, p. 2663 - 2674 (2007/10/02)
Lithium t-butyl hydroperoxide (easily generated by addition of an alkyl-lithium to anhydrous t-butyl hydroperoxide in THF solution) is a powerful reagent for the epoxidation of electrophilic alkenes at -20 to 0 °C under full stereocontrol. Thus αβ-unsaturated esters, sulphones, sulphoximines, and amides are readily epoxidised with complete regio- and stereo-specificity and with considerable chiroselectivity (20-100%) when appropriate chiral auxiliaries such as menthyl, 8-phenylmenthyl, or a camphor-sulphonamide derivative are used. Asymmetric αβ-unsaturated sulphoximines undergo epoxidation with 100% diastereoselectivity. The only exceptions to stereocontrol noted are heavily substituted maleate esters such as di-t-butyl maleate. The αβ-epoxy amides are shown to be valuable sources of the corresponding epoxy ketones by treatment with an organolithium, allowing a stereo- and chemoselective entry in high yield to these useful intermediates.
A Powerful New Stereo-controlled Method for Epoxidation of Electrophilic Alkenes
Clark, Carol,Hermans, Patricia,Meth-Cohn, Otto,Moore, Clive,Taljaard, Heinrich C.,Vuuren, Gerda van
, p. 1378 - 1380 (2007/10/02)
t-Butyl hydroperoxide and an alkyl-lithium in dry tetrahydrofuran are shown to epoxidise α,β-unsaturated esters and sulphones efficiently in a stereo- and regio-specific manner, while esters of chiral alcohols undergo diasterefacially selective epoxidatio
