First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13238 - 13341

Published: Oct. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Language: Английский

---

Copper-Catalyzed Borylative Difunctionalization of π-Systems

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(19), P. 11578 - 11622

Published: Aug. 25, 2020

Organoboronates represent a cornerstone functional group in modern synthesis owing to their unique reactivity and divergent synthetic capability. Copper catalysis has become one of the most powerful methods stereoselectively install boron across diverse π-systems. Additionally, this method affords tremendous versatility enabled by difunctionalization π-system addition an electrophile. This review covers known electrophiles intercept catalytic intermediates borylative strategies that have been reported up end May 2020.

Language: Английский

---

Photoinduced Copper‐Catalyzed Asymmetric Three‐Component Coupling of 1,3‐Dienes: An Alternative to Kharasch–Sosnovsky Reaction

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(42), P. 22956 - 22962

Published: Aug. 18, 2021

Abstract Kharasch–Sosnovsky reaction is one of the most powerful methods for allylic oxidation alkenes. However, inherent radical mechanism and use peroxides as both oxidants oxygen nucleophiles render dearth universal catalytic systems highly enantioselective variants limited scope. Herein, an alternative to asymmetric that utilized a chiral copper catalyst purple‐LED irradiation enable three‐component coupling 1,3‐dienes, oxime esters, carboxylic acids reported. This protocol features mild conditions, remarkable scope functional group tolerance evidenced by >80 examples utility in late‐stage modification pharmaceuticals natural products. Detailed mechanistic studies provide evidences radical‐based pathway.

Language: Английский

---

Catalytic Asymmetric Hydroalkoxylation and Formal Hydration and Hydroaminoxylation of Conjugated Dienes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3915 - 3925

Published: Feb. 10, 2023

The straightforward construction of stereogenic centers bearing unprotected functional groups, as in nature, has been a persistent pursuit synthetic chemistry. Abundant applications free enantioenriched allyl alcohol and hydroxylamine motifs have made the asymmetric hydration hydroaminoxylation conjugated dienes from water hydroxylamine, respectively, intriguing efficient routes that have, however, unachievable thus far. A fundamental challenge is failure to realize transition-metal-catalyzed enantioselective C–O bond constructions via hydrofunctionalization dienes. Here, we perform comprehensive study toward stereoselective formal by synthesizing set new P,N-ligands identifying an aryl-derived oxime surrogate for both hydroxylamine. Asymmetric hydroalkoxylation with also elucidated. Furthermore, versatile derivatizations following provide indirect but concise hydrophenoxylation, hydrofluoroalkoxylation, hydrocarboxylation unreported Finally, ligand-to-ligand hydrogen transfer process proposed based on results preliminary mechanistic experiments.

Language: Английский

---

Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2919 - 2927

Published: Jan. 26, 2024

Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, the polymer industry. Although catalytic dicarboxylation with CO2 represents a straightforward sustainable route to dicarboxylic acids, it is still highly challenging limited generation of achiral or racemic acids. To date, asymmetric give chiral has not been reported. Herein, we report first 1,3-dienes via Cu catalysis. This strategy provides an efficient environmentally benign high regio-, chemo-, enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation carboxylated allyl boronic ester intermediates subsequent carboxylation C–B bonds dicarboxylates, key success this dicarboxylation. Moreover, protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, facile synthesis liquid crystalline polyester drug-like scaffolds.

Language: Английский

---

Enantioselective Synthesis of Axially Chiral Alkylidenecycloalkanes via Copper-Catalyzed Functionalization of Acyl Allenols

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2351 - 2358

Published: Jan. 24, 2025

Language: Английский

---

Copper-catalyzed functionalization of enynes

Chemical Science, Journal Year: 2020, Volume and Issue: 11(42), P. 11380 - 11393

Published: Jan. 1, 2020

The copper-catalyzed functionalization of enyne derivatives has recently emerged as a powerful approach in contemporary synthesis. Enynes are versatile and readily accessible substrates that can undergo variety reactions to yield densely functionalized, enantioenriched products. In this perspective, we review transformations enynes, such boro- hydrofunctionalizations, copper-mediated radical difunctionalizations, cyclizations. Particular attention is given the regiodivergent 1,3-enynes, current mechanistic understanding processes.

Language: Английский

---

Catalyst-controlled enantioselective 1,1-arylboration of unactivated olefins

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(11), P. 951 - 958

Published: Oct. 19, 2020

Language: Английский

---

Beyond Carbon: Enantioselective and Enantiospecific Reactions with Catalytically Generated Boryl- and Silylcopper Intermediates

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(7), P. 1070 - 1081

Published: July 9, 2020

Catalytic asymmetric C–C bond formation with alkylcopper intermediates as carbon nucleophiles is now textbook chemistry. Related chemistry boron and silicon where the boryl- accordingly silylcopper are catalytically regenerated from bench-stable pronucleophiles had been underdeveloped for years or did not even exist until recently. Over past decade, copper catalysis employing those main-group elements rapidly transformed into a huge field in its own right an impressive breadth of enantioselective C–B C–Si bond-forming reactions, respectively. Its current state art does have to shy away comparison that boron's silicon's common neighbor periodic table, carbon. This Outlook meant be detailed summary manifold advances. It rather aims at providing brief conceptual what forms basis latest exciting progress, especially area three-component reactions cross-coupling reactions.

Language: Английский

---

Allenes and Dienes as Chiral Allylmetal Pronucleophiles in Catalytic Enantioselective C=X Addition: Historical Perspective and State‐of‐The‐Art Survey

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(52), P. 13107 - 13116

Published: June 29, 2021

Abstract The use of allenes and 1,3‐dienes as chiral allylmetal pronucleophiles in intermolecular catalytic enantioselective reductive additions to aldehydes, ketones, imines, carbon dioxide other C=X electrophiles is exhaustively catalogued together with redox‐neutral hydrogen auto‐transfer processes. Coverage limited processes that result both C−H C−C bond formation. alkynes latent multicomponent allylations involving dienes not covered. As illustrated this review, the ability serve tractable non‐metallic has evoked many useful transformations have no counterpart traditional chemistry.

Language: Английский

---