16487-65-3Relevant articles and documents
METHODS OF BORYLATION AND USES THEREOF
-
Page/Page column 61-62, (2021/04/30)
The present invention relates, in general terms, to methods of borylation and uses thereof. In particular, the present invention provides a method of borylating an alkene compound by contacting the compound with a boron compound, a Fe pre-catalyst and a protic additive. The borylation occurs at a vicinal (β) position to an electron donating or electron withdrawing moiety of the compound.
Structural elucidation of a methylenation reagent of esters: Synthesis and reactivity of a dinuclear titanium(iii) methylene complex
Kurogi, Takashi,Kuroki, Kaito,Moritani, Shunsuke,Takai, Kazuhiko
, p. 3509 - 3515 (2021/03/29)
Transmetallation of a zinc methylene complex [ZnI(tmeda)]2(μ-CH2) with a titanium(iii) chloride [TiCl3(tmeda)(thf)] produced a titanium methylene complex. The X-ray diffraction study displayed a dinuclear methylene structure [TiCl(tmeda)]2(μ-CH2)(μ-Cl)2. Treatment of an ester with the titanium methylene complex resulted in methylenation of the ester carbonyl to form a vinyl ether. The titanium methylene complex also reacted with a terminal olefin, resulting in olefin-metathesis and olefin-homologation. Cyclopropanation by methylene transfer from the titanium methylene proceeded by use of a 1,3-diene. The mechanistic study of the cyclopropanation reaction by the density functional theory calculations was also reported.
Iron-Catalyzed Tunable and Site-Selective Olefin Transposition
Yu, Xiaolong,Zhao, Haonan,Li, Ping,Koh, Ming Joo
supporting information, p. 18223 - 18230 (2020/12/04)
The catalytic isomerization of C-C double bonds is an indispensable chemical transformation used to deliver higher-value analogues and has important utility in the chemical industry. Notwithstanding the advances reported in this field, there is compelling demand for a general catalytic solution that enables precise control of the C═C bond migration position, in both cyclic and acyclic systems, to furnish disubstituted and trisubstituted alkenes. Here, we show that catalytic amounts of an appropriate earth-abundant iron-based complex, a base and a boryl compound, promote efficient and controllable alkene transposition. Mechanistic investigations reveal that these processes likely involve in situ formation of an iron-hydride species which promotes olefin isomerization through sequential olefin insertion/β-hydride elimination. Through this strategy, regiodivergent access to different products from one substrate can be facilitated, isomeric olefin mixtures commonly found in petroleum-derived feedstock can be transformed to a single alkene product, and unsaturated moieties embedded within linear and heterocyclic biologically active entities can be obtained.