Recent advances in nickel-catalyzed asymmetric hydrofunctionalization of alkenes

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 3140 - 3162

Published: Nov. 1, 2022

Language: Английский

---

Stereodivergent, Kinetically Controlled Isomerization of Terminal Alkenes via Nickel Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 18, 2024

Abstract Because internal alkenes are more challenging synthetic targets than terminal alkenes, metal‐catalyzed olefin mono‐transposition (i.e., positional isomerization) approaches have emerged to afford valuable E ‐ or Z‐ from their complementary alkene feedstocks. However, the applicability of these methods has been hampered by lack generality, commercial availability precatalysts, and scalability. Here, we report a nickel‐catalyzed platform for stereodivergent / Z ‐selective synthesis at room temperature. Commercial reagents enable this one‐carbon transposition ‐internal via Ni−H‐mediated insertion/elimination mechanism. Though mechanistic regime is same in both systems, underlying pathways that lead each active catalysts distinct, with catalyst forming comproportionation an oxidative addition complex followed substrate protonation metal trialkylphosphonium salt additive. In case, ligand sterics denticity control stereochemistry prevent over‐isomerization.

Language: Английский

---

Nickel-Catalyzed Remote C(sp³)–N/O Bond Formation of Alkenes with Unactivated Amines and Alcohols

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4409 - 4420

Published: March 17, 2023

Transition metal-catalyzed remote hydrofunctionalization of alkenes is an efficient method to realize C(sp3)–H functionalization. However, with unactivated amines and alcohols has not been successfully developed date. Herein, we report nickel-catalyzed hydroamination hydroetherification alcohols, accessing a series gem-diamine N,O-acetal derivatives in good high yields (up 93%) exclusive regioselectivities. The mechanistic investigations DFT computations indicated that the use 2-iodo-2-methylpropane (tBuI) as both mild hydride source radical precursor was essential afford functionalized products. This research work provides install amino or alkoxyl group at position far from double bond alkenes.

Language: Английский

---

Alkene Isomerization Using a Heterogeneous Nickel-Hydride Catalyst

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15596 - 15608

Published: May 21, 2024

Transition metal-catalyzed alkene isomerization is an enabling technology used to install distal its original site. Due their well-defined structure, homogeneous catalysts can be fine-tuned optimize reactivity, stereoselectivity, and positional selectivity, but they often suffer from instability nonrecyclability. Heterogeneous are generally highly robust continue lack active-site specificity challenging rationally improve through structural modification. Known single-site heterogeneous for utilize precious metals bespoke, expensive, synthetically intense supports. Additionally, have mediocre inspiring us develop a catalyst with active site made readily available compounds of Earth-abundant elements. Previous work demonstrated that very formed upon protonation Ni[P(OEt)3]4 by H2SO4, generating [Ni–H]+ This incredibly active, also decomposes readily, which severely limits utility. Herein we show using solid acid (sulfated zirconia, SZO300), not only this decomposition prevented, high activity maintained, improved selectivity achieved, broader scope functional groups tolerated. Preliminary mechanistic experiments suggest the catalytic reaction likely goes intermolecular, two-electron pathway. A detailed kinetic study comparing state-of-the-art Ni Pd reveals highest seen Ni/SZO300 system. The reactivity Ni/SZO300, limited isomerization; it competent hydroalkenylation, hydroboration, hydrosilylation, demonstrating broad application catalyst.

Language: Английский

---

Nickel-catalyzed hydroarylation reaction: a useful tool in organic synthesis

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 5074 - 5103

Published: Jan. 1, 2022

The nickel-catalyzed hydroarylation reaction opens up new routes to access complex organic compounds in a highly regio and stereoselective fashion from easily available precursors, such as olefin, alkyne, arene, aryl halide, boronic acid.

Language: Английский

---

Ligand-enabled Ni-catalyzed hydroarylation and hydroalkenylation of internal alkenes with organoborons

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 12, 2022

The transition metal-catalyzed hydrofunctionalization of alkenes offers an efficient solution for the rapid construction complex functional molecules, and significant progress has been made during last decades. However, internal remains a challenge due to low reactivity difficulties controlling regioselectivity. Here, we report hydroarylation hydroalkenylation lacking directing group with aryl alkenyl boronic acids in presence nickel catalyst, featuring broad substrate scope wide tolerance under redox-neutral conditions. key achieving this reaction is identification bulky 1-adamantyl β-diketone ligand, which capable overcoming 1,2-disubstituted alkenes. Preliminary mechanistic studies unveiled that undergoes Ar-Ni(II)-H initiated process, generated by oxidative addition alcoholic solvent Ni(0) species sequential transmetalation. In addition, proves be turnover-limiting step.

Language: Английский

---

Switching between Hydrogenation and Olefin Transposition Catalysis via Silencing NH Cooperativity in Mn(I) Pincer Complexes

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10818 - 10825

Published: Aug. 19, 2022

While Mn-catalyzed (de)hydrogenation of carbonyl derivatives has been well established, the reactivity Mn hydrides with olefins remains very rare. Herein, we report a Mn(I) pincer complex that effectively promotes site-controlled transposition olefins. This is shown to emerge once N-H functionality within Mn/NH bifunctional suppressed by alkylation. detrimental for (de)hydrogenation, such masking cooperative allows highly efficient conversion wide range allylarenes higher-value 1-propenybenzenes in near-quantitative yield excellent stereoselectivities. The toward single positional isomerization was also retained long-chain alkenes, resulting regioselective formation 2-alkenes, which are less thermodynamically stable compared other possible products. detailed mechanistic analysis reaction between activated catalyst and points catalysis operating via metal-alkyl mechanism-one three conventional mechanisms previously unknown complexes.

Language: Английский

---

Iron‐Catalyzed Positional and Geometrical Isomerization of Alkenes

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(8), P. 1100 - 1111

Published: Feb. 20, 2023

Abstract This review outlines the most noteworthy achievements of last few years in renascent field positional and geometrical isomerization alkenes using iron catalysis, from a mechanistic perspective. Particular attention will be placed on developments beyond seminal contributions carbonyl complexes their aspects underlying nature active species. The relevant literature has been covered until late 2022. magnified image

Language: Английский

---

Modular Ni(0)/Silane Catalytic System for the Isomerization of Alkenes

Organometallics, Journal Year: 2022, Volume and Issue: 41(4), P. 486 - 496

Published: Feb. 16, 2022

Alkenes are used ubiquitously as starting materials and synthetic targets in all areas of chemistry. Controlling their geometry position along a chain is vital to reactivity properties yet remains challenging. Alkene isomerization an atom-economical process synthesize targeted alkenes, selectivity can be controlled using transition metal catalysts. The development mild, selective has enabled efficient tandem catalytic systems for the remote functionalization which alkene isomerized new prior step. key challenges developing catalysts applications (i) lack modularity catalyst structure (ii) requirement nonmodular and/or harsh additives during activation. We address both with modular (NHC)Ni(0)/silane system (NHC, N-heterocyclic carbene), demonstrating use triaryl silanes readily accessible (NHC)Ni(0) complexes form proposed active (NHC)(silyl)Ni–H species situ. show that modification steric electronic nature via ancillary ligand silane partner, respectively, easily achieved, creating uniquely versatile effective formation internal alkenes high yield E-alkene. mild activators enables substrates variety functional groups, including acid-labile groups. broad substrate scope, by design, makes this strong candidate applications. Preliminary mechanistic studies support Ni–H insertion/elimination pathway.

Language: Английский

---

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 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.

Language: Английский

---