50663-21-3Relevant articles and documents
Acid- And base-switched palladium-catalyzed γ-C(sp3)-H alkylation and alkenylation of neopentylamine
Zhang, Jinquan,Zhang, Shuaizhong,Zou, Hongbin
supporting information, p. 3466 - 3471 (2021/05/31)
The functionalization of remote unactivated C(sp3)-H and the reaction selectivity are among the core pursuits for transition-metal catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)-H-selective alkylation and alkenylation with removable 7-azaindole as a directing group. Acid and base were found to be the decisive regulators for the selective alkylation and alkenylation, respectively, on the same single substrate under otherwise the same reaction conditions. Various acrylates were compatible for the formation of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. The alkenylation protocol could be further extended to acrylates with natural product units and α,β-unsaturated ketones. The preliminary synthetic manipulation of the alkylation and alkenylation products demonstrates the potential of this strategy for structurally diverse aliphatic chain extension and functionalization. Mechanistic experimental studies showed that the acidic and basic catalytic transformations shared the same six-membered dimer palladacycle.
Photoredox/Cobalt Dual Catalysis for Visible-Light-Mediated Alkene-Alkyne Coupling
Rai, Pramod,Maji, Kakoli,Maji, Biplab
supporting information, p. 3755 - 3759 (2019/05/24)
Dual photoredox transition-metal catalysis has recently emerged as a powerful tool for making synthetically challenging carbon-carbon bonds under milder reaction conditions. Herein, we report on the visible-light-mediated controlled generation of low-valent cobalt catalyst without the need for a metallic reductant. It enabled C-C bond formation via ene-yne coupling at room temperature. The generality of this dual catalysis is demonstrated via the creation of sizable molecular diversity with the accommodation of several functional groups.
Ti-Catalyzed Radical Alkylation of Secondary and Tertiary Alkyl Chlorides Using Michael Acceptors
Wu, Xiangyu,Hao, Wei,Ye, Ke-Yin,Jiang, Binyang,Pombar, Gisselle,Song, Zhidong,Lin, Song
supporting information, p. 14836 - 14843 (2018/11/10)
Alkyl chlorides are common functional groups in synthetic organic chemistry. However, the engagement of unactivated alkyl chlorides, especially tertiary alkyl chlorides, in transition-metal-catalyzed C-C bond formation remains challenging. Herein, we describe the development of a TiIII-catalyzed radical addition of 2° and 3° alkyl chlorides to electron-deficient alkenes. Mechanistic data are consistent with inner-sphere activation of the C-Cl bond featuring TiIII-mediated Cl atom abstraction. Evidence suggests that the active TiIII catalyst is generated from the TiIV precursor in a Lewis-acid-assisted electron transfer process.
