Enantioselective Hydroalkenylation of Olefins with Enol Sulfonates Enabled by Dual Copper Hydride and Palladium Catalysis

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(14), С. 5330 - 5335

Опубликована: Март 30, 2021

The catalytic enantioselective synthesis of α-chiral olefins represents a valuable strategy for rapid generation structural diversity in divergent syntheses complex targets. Herein, we report protocol the dual CuH- and Pd-catalyzed asymmetric Markovnikov hydroalkenylation vinyl arenes anti-Markovnikov unactivated olefins, which readily available enol triflates can be utilized as alkenyl coupling partners. This method allowed diverse including tri- tetrasubstituted olefin products, are challenging to prepare by existing approaches.

Язык: Английский

---

Ni-catalyzed hydroalkylation of olefins with N-sulfonyl amines

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Окт. 7, 2021

Hydroalkylation, the direct addition of a C(sp3)-H bond across an olefin, is desirable strategy to produce valuable, complex structural motifs in functional materials, pharmaceuticals, and natural products. Herein, we report reliable method for accessing α-branched amines via nickel-catalyzed hydroalkylation reactions. Specifically, by using bis(cyclooctadiene)nickel (Ni(cod)2) together with phosphine ligand, achieved formal insertion reaction between olefins N-sulfonyl without need external hydride source. The amine not only provides alkyl motif but also delivers olefin means nickel-engaged β-hydride elimination/reductive elimination process. This platform constructing chiral P-chiral demonstrating its potential utility organic synthesis. Notably, sulfonamidyl boronate formed situ under basic conditions promotes ring-opening azanickellacycle intermediate, leading significant improvement catalytic efficiency.

Язык: Английский

---

Facile Synthesis of Chiral α‐Hydroxy Ketones by a Ni‐Catalyzed Multicomponent Hydrometallation–CO Insertion–Enantioconvergent Alkylation Cascade

Chinese Journal of Chemistry, Год журнала: 2022, Номер 41(3), С. 294 - 300

Опубликована: Окт. 17, 2022

Comprehensive Summary NiH‐catalyzed multicomponent reductive hydrofunctionalization of alkenes is an attractive but poorly explored approach to rapidly increasing molecular complexity. In this process, the selective generation desired product can be challenging. Herein, we report that a highly chemo‐, regio‐ and enantioselective hydrocarbonylation has been achieved using chloroformate ester as source CO. A wide range structurally diverse α‐hydroxy ketones, privileged structural elements in bioactive molecules useful building blocks, were obtained from such reactions with high enantiomeric purity.

Язык: Английский

---

Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Год журнала: 2020, Номер 24(6), С. 909 - 915

Опубликована: Май 14, 2020

Nonprecious metal catalysis is a highly active area of research for both industrial and academic laboratories. New methods that efficiently generate useful functionality in cost-effective, high yielding, environmentally friendly ways naturally garner attention from process chemists many different industries. This series highlights summarizes literature on the general topic nonprecious over four-month timeframes will focus major trends field are interest pharmaceutical industry. The first installment selected transformations using copper, nickel, iron catalysts.

Язык: Английский

---

Diphosphine Ligand‐Enabled Nickel‐Catalyzed Chelate‐Assisted Inner‐Selective Migratory Hydroarylation of Alkenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(1)

Опубликована: Ноя. 21, 2023

The precise control of the regioselectivity in transition metal-catalyzed migratory hydrofunctionalization alkenes remains a big challenge. With transient ketimine directing group, nickel-catalyzed β-selective hydroarylation and hydroalkenylation alkenyl ketones has been realized with aryl boronic acids using alkyl halide as mild hydride source for first time. key to this success is use diphosphine ligand, which capable generation Ni(II)-H species presence bromide, enabling efficient insertion alkene into sequent rapid chain walking process. present approach diminishes organosilanes reductant, tolerates wide array complex functionalities excellent regioselective control. Moreover, catalytic system could also be applied azahetereoarenes, thus providing general preparation 1,2-aryl heteroaryl motifs potential applications pharmaceutical discovery.

Язык: Английский

---