768-56-9Relevant articles and documents
Paramagnetische 17-Elektronen-+-Komplexe; Synthese, Struktur und katalysche Anwendung
Sernau, Volker,Huttner, Gottfried,Fritz, Martin,Zsolnai, Laszlo,Walter, Olaf
, p. C23 - C29 (1993)
The paramagnetic 17-electron η3-allylic complexes 3-Allyl)>+ (Tripod = CH3C(CH2PPh2)3; Allyl = C3H5, 2a; CH2C(CH3)CH2, 2b; (CH3)CHCHCH2, 2c) have been obtained from (Tripod)Co(η2-O2CCH3)+, 1, as crystalline BPh4-salts.The compounds have been characterized by X-ray analyses as well as by usual techniques including ESR.Compounds 2 have been found to act as effective catalysts for allylic alkylations.As an example the catalytic formation of 4-phenylbutene-1 is given.
Olefination via Cu-Mediated Dehydroacylation of Unstrained Ketones
Dong, Guangbin,Xu, Yan,Zhou, Xukai
supporting information, p. 20042 - 20048 (2021/12/03)
The dehydroacylation of ketones to olefins is realized under mild conditions, which exhibits a unique reaction pathway involving aromatization-driven C-C cleavage to remove the acyl moiety, followed by Cu-mediated oxidative elimination to form an alkene between the α and β carbons. The newly adopted N′-methylpicolinohydrazonamide (MPHA) reagent is key to enable efficient cleavage of ketone C-C bonds at room temperature. Diverse alkyl- and aryl-substituted olefins, dienes, and special alkenes are generated with broad functional group tolerance. Strategic applications of this method are also demonstrated.
Designed electron-deficient gold nanoparticles for a room-temperature Csp3-Csp3coupling reaction
Yu, Qiu-Ying,Su, Hui,Zhai, Guang-Yao,Zhang, Shi-Nan,Sun, Lu-Han,Chen, Jie-Sheng,Li, Xin-Hao
supporting information, p. 741 - 744 (2021/02/06)
Stille cross-coupling reactions catalysed by an ideal catalyst combining the high activity of homogeneous catalysts and the reusability of heterogeneous catalysts are of great interest for C-C bond formation, which is a widely used reaction in fine chemistry. Despite great effort to increase the utilization ratio of surface metal atoms, the activity of heterogeneous catalysts under mild conditions remains unsatisfactory. Herein, we design a proof-of-concept strategy to trigger the room-temperature activity of heterogeneous Au catalysts by decreasing the electron density at the interface of a rationally designed Schottky heterojunction of Au metals and boron-doped carbons. The electron-deficient Au nanoparticles formed as a result of the rectifying contact with boron-doped carbons facilitate the autocleavage of C-Br bonds for highly efficient C-C coupling reactions of alkylbromides and allylstannanes with a TOF value of 5199 h-1 at room temperature, surpassing that of the state-of-the-art homogeneous catalyst. This journal is
Exploiting the radical reactivity of diazaphosphinanes in hydrodehalogenations and cascade cyclizations
Cheng, Jin-Pei,Yang, Jin-Dong,Zhang, Jingjing
, p. 4786 - 4790 (2020/06/18)
The remarkable reducibility of diazaphosphinanes has been extensively applied in various hydrogenations, based on and yet limited by their well-known hydridic reactivity. Here we exploited their unprecedented radical reactivity to implement hydrodehalogenations and cascade cyclizations originally inaccessible by hydride transfer. These reactions feature a broad substrate scope, high efficiency and simplicity of manipulation. Mechanistic studies suggested a radical chain process in which a phosphinyl radical is generated in a catalytic cycle via hydrogen-atom transfer from diazaphosphinanes. The radical reactivity of diazaphosphinanes disclosed here differs from their well-established hydridic reactivity, and hence, opens a new avenue for diazaphosphinane applications in organic syntheses.
