928-92-7Relevant articles and documents
Ionic Iodocarbocyclization Reactions of 4-Alkenyl- and 4-Alkynylmalonate Derivatives
Kitagawa, Osamu,Inoue, Tadashi,Hirano, Keiko,Taguchi, Takeo
, p. 3106 - 3112 (1993)
The cyclization reactions of dimethyl 4-alkenylmalonate derivatives 1a-d in the presence of I2 and Ti(Ot-Bu)4 proceed in a highly regio- and stereocontrolled manner (5-exo cyclization and trans addition) to give (iodoalkyl)cyclopentane derivatives 2 or bicyclic lactones 3 through the displacement of the iodide of 2 by an ester group.Iodocarbocyclization reactions of dimethyl malonates 1g-i or dimethyl malonates 1j and 1k proceed regio- and stereoselectively to give fused ring compounds or spiro compounds, respectively, as single isomers.Similar reactions of 4-alkynyl derivatives 5 give preferentially E-iodomethylene cyclopentane derivatives 6.An ionic mechanism rather than a radical mechanism is suggested on the basis of the regioselectivity and stereospecificity of the above reactions.
Cobalt-Catalyzed Intermolecular Hydrofunctionalization of Alkenes: Evidence for a Bimetallic Pathway
Zhou, Xiao-Le,Yang, Fan,Sun, Han-Li,Yin, Yun-Nian,Ye, Wei-Ting,Zhu, Rong
supporting information, p. 7250 - 7255 (2019/05/16)
A functional group tolerant cobalt-catalyzed method for the intermolecular hydrofunctionalization of alkenes with oxygen- and nitrogen-based nucleophiles is reported. This protocol features a strategic use of hypervalent iodine(III) reagents that enables a mechanistic shift from conventional cobalt-hydride catalysis. Key evidence was found supporting a unique bimetallic-mediated rate-limiting step involving two distinct cobalt(III) species, from which a new carbon-heteroatom bond is formed.
Total Synthesis and Biological Evaluation of Siladenoserinol A and its Analogues
Yoshida, Masahito,Saito, Koya,Kato, Hikaru,Tsukamoto, Sachiko,Doi, Takayuki
supporting information, p. 5147 - 5150 (2018/03/26)
The total synthesis of siladenoserinol A, an inhibitor of the p53–Hdm2 interaction, has been achieved. AuCl3-catalyzed hydroalkoxylation of an alkynoate derivative smoothly and regioselectively proceeded to afford a bicycloketal in excellent yield. A glycerophosphocholine moiety was successfully introduced through the Horner–Wadsworth–Emmons reaction using an originally developed phosphonoacetate derivative. Finally, removal of the acid-labile protecting groups, followed by regioselective sulfamate formation of the serinol moiety afforded the desired siladenoserinol A, and benzoyl and desulfamated analogues were also successfully synthesized. Biological evaluation showed that the sulfamate is essential for biological activity, and modification of the acyl group on the bicycloketal can improve the inhibitory activity against the p53–Hdm2 interaction.
Pd(II)-Catalyzed [4 + 2] Heterocyclization Sequence for Polyheterocycle Generation
Glaisyer, Elizabeth L.,Watt, Michael S.,Booker-Milburn, Kevin I.
supporting information, p. 5877 - 5880 (2018/09/25)
A new Pd(II)-catalyzed cascade sequence for the formation of polyheterocycles, from simple starting materials, is reported. The sequence is applicable to both indole and pyrrole substrates, and a range of substituents are tolerated. The reaction is thought to proceed by a Pd(II)-catalyzed C-H activated Heck reaction followed by a second Pd(II)-catalyzed aza-Wacker reaction with two Cu(II)-mediated Pd(0) turnovers per sequence. The sequence can be considered a formal [4 + 2] heterocyclization.