Recent Advances in Mono‐ and Difunctionalization of Unactivated Olefins

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(12), P. 3201 - 3232

Published: Nov. 5, 2021

Abstract Olefins are synthetically useful building blocks in modern organic synthesis. Direct functionalization of olefins; represent one the most explored transformations synthetic chemistry due to their easy availability and reactivity towards large number reactants affording diverse range compounds. In recent times, development new protocols for olefins is a growing realm. A plethora olefin methodologies have been reported literature through ionic free radical mechanisms including single electron transfer (SET) last two decades. This review gives an overview mono‐ difunctionalization unactivated olefins, with emphasis on mechanistic details.

Language: Английский

---

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(41), P. 22454 - 22460

Published: Aug. 4, 2021

Abstract Regiodivergent addition reactions provide straightforward and atom‐economic approaches to access different regioisomers. However, the regio‐chemistry control all possible results is still challenging especially for reaction involving multiple steps. Herein, we reported regio‐controllable cobalt‐catalyzed sequential hydrosilylation/hydroboration of arylacetylenes, delivering regio‐outcomes with high regioselectivities (up >20/1 rr cases). Each regioisomer value‐added silylboronates could be efficiently regioselectively obtained from same materials. The adjustment ligands cobalt catalysts combined dual catalysis relay strategy key achieve control. This research might inspire exploration diversity‐oriented synthesis that involves additions full sets regioisomers other synthetic useful molecules.

Language: Английский

---

Deoxygenative Haloboration and Enantioselective Chloroboration of Carbonyls

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(50), P. 22870 - 22876

Published: Dec. 7, 2022

Deoxygenative difunctionalization of carbonyls affords a straightforward and effective route to construct geminal dual functionalized motifs. However, the research in this field is very challenging due strong bond dissociation energies C–O double or subsequently formed bond. Herein, we report highly efficient deoxygenative haloboration aldehydes generate secondary α-haloboronates. Meanwhile, difficult-to-obtain tertiary α-haloboronates can be also readily prepared via same strategy with ketones. Furthermore, enantioselective chloroboration was successfully achieved give chiral α-chloroboronates, important intermediates access enantioenrich multisubstituted stereocenters. These versatile products surprisingly attained through simple mild process remarkable substrate scope expansion functional group tolerance. Additionally, these reactions proceed well on large scales, giving more practical values application.

Language: Английский

---

Metal-free radical difunctionalization of ethylene

Chem, Journal Year: 2022, Volume and Issue: 9(2), P. 472 - 482

Published: Nov. 9, 2022

Language: Английский

---

Nickel-Catalyzed 1,1-Aminoborylation of Unactivated Terminal Alkenes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(8), P. 5538 - 5543

Published: April 10, 2023

Herein, we disclose a Ni-catalyzed 1,1-difunctionalization of unactivated terminal alkenes that enables the incorporation two different heteroatom motifs across an olefin backbone, thus streamlining access to α-aminoboronic acid derivatives from simple precursors. The method is characterized by its simplicity and generality wide number coupling counterparts.

Language: Английский

---

Radical Decyanations of Unactivated Carbon‐CN Bonds: Recent Achievements and Mechanistic Studies

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(13), P. 2058 - 2091

Published: May 17, 2023

Abstract Decyanation is an important process in the synthesis of aromatic molecules studies pharmaceutical research, medical and materials sciences. In late‐stage modifications privileged carbo/heterocyclic scaffolds, radical‐type decyanation techniques have been devised to date. As a result, chemistry cyano‐involved conversions, hotly debated subject over past few decades, has advanced significantly. The cyano group (CN), on other hand, rarely acknowledged as good reaction site due its thermodynamic robustness. most recent advancements catalytic radical protocols that CN behaved leaving made are surveyed this article. Following introduction number different modes, reactions used activate C−CN bonds primarily categorized, text herein divided into three groups: (1) photo‐catalyzed transformations, (2) electro‐catalyzed (3) transition‐metal‐catalyzed or metal‐free transformations. With emphasis systems synthetic applications bond activation, review will provide readers with overview reactions.

Language: Английский

---

Triply Selective & Sequential Diversification at C_sp³: Expansion of Alkyl Germane Reactivity for C−C & C−Heteroatom Bond Formation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 22, 2024

Abstract We report the triply selective and sequential diversification of a single C sp 3 carbon carrying Cl, Bpin GeEt for modular programmable construction ‐rich molecules. Various functionalizations −Cl −BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by −GeEt group. Moreover, methodological repertoire alkyl germane functionalization was significantly expanded beyond hitherto known Giese addition arylation to alkynylation, alkenylation, cyanation, halogenation, azidation, C−S bond formation as well first demonstration stereo‐selective ‐[Ge] bond.

Language: Английский

---

A new avenue for the preparation of organoboron compounds via nickel catalysis

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 448, P. 214165 - 214165

Published: Aug. 29, 2021

Language: Английский

---

Redox-Neutral Ni-Catalyzed sp³ C–H Alkylation of α-Olefins with Unactivated Alkyl Bromides

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(7), P. 3815 - 3820

Published: March 14, 2022

A light-induced redox-neutral Ni-catalyzed sp3 C–H alkylation of unactivated alkenes with alkyl bromides possessing β-hydrogens is described herein. The method distinguished by its simplicity, wide scope, and exquisite regio- chemoselectivity profile, thus offering an entry point to forge sp3–sp3 architectures.

Language: Английский

---

Site-Selective Functionalization of C(sp³) Vicinal Boronic Esters

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(17), P. 10603 - 10620

Published: Aug. 15, 2022

Selective functionalization of the C–B bond in 1,2-bis(boronate) esters has emerged as a powerful tool to prepare 1,2-difunctionalized compounds with stereocontrol. Suzuki cross-coupling, oxidation, amination, and homologation reactions serve platforms wide variety from common intermediate. The exquisite selectivity offered their easy preparation feedstock material using myriad catalytic transformations make them attractive building blocks for complex molecules. In this Perspective, we summarize examples selective vicinal bis(boronates), attending nature functionalization.

Language: Английский

---