Methodologies and Strategies for Selective Borylation of C–Het and C–C Bonds

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(15), P. 7348 - 7398

Published: June 29, 2020

Organoborons have emerged as versatile building blocks in organic synthesis to achieve molecular diversity and carboxylic acid bioisosteres with broad applicability drug discovery. Traditionally, these compounds are prepared by the substitution of Grignard/lithium reagents electrophilic boron species Brown hydroboration. Recent developments provided new routes for efficient preparation organoborons applying reactions using chemical feedstocks leaving groups. As compared previous methods that used halides (I, Br, Cl), direct borylation less reactive C–Het C–C bonds has become highly important get efficiency functional-group compatibility. This Review aims provide a comprehensive overview this topic, including (1) C–F bond borylation, (2) C–O (3) C–S (4) C–N (5) borylation. Considerable attention is given strategies mechanisms involved. We expect will inspire chemists discover more transformations expand field.

Language: Английский

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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

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Recent advance in the C–F bond functionalization of trifluoromethyl-containing compounds

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(14), P. 3915 - 3942

Published: Jan. 1, 2021

The C–F bond is the strongest single in organic compounds.

Language: Английский

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Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 364(2), P. 234 - 267

Published: Nov. 29, 2021

Abstract Fluorine‐containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures of immense interest fields organic synthesis medicinal chemistry. Among various fluorinated groups, difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for difluoromethylated compounds have been rapidly developed. However, most treat aromatic with excess difluoromethylating reagents, which often contain organometallic compounds, so transformations generally less environmentally friendly atom‐economical. this review, we summarize development new motifs or difluoroalkenes from trifluoromethylated trifluoromethyl alkenes via single C( sp 3 )−F bond cleavage. magnified image

Language: Английский

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Synthetic Advantages of Defluorinative C−F Bond Functionalization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Aug. 22, 2023

Abstract Much progress has been made in the development of methods to both create compounds that contain C−F bonds and functionalize bonds. As such, are becoming common versatile synthetic functional handles. This review summarizes advantages defluorinative functionalization reactions for small molecule synthesis. The coverage is organized by type carbon framework fluorine attached mono‐ polyfluorinated motifs. main challenges, opportunities advances discussed each class organofluorine. Most text focuses on case studies illustrate how defluorofunctionalization can improve routes targets or properties enable unique mechanisms reactions. broader goal showcase incorporating exploiting design routes, improvement specific advent new methods.

Language: Английский

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Catalytic Regio- and Enantioselective Boracarboxylation of Arylalkenes with CO₂ and Diboron

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2888 - 2894

Published: Jan. 26, 2024

Catalytic asymmetric carboxylation of readily available alkenes with CO2, an abundant and sustainable one-carbon building block, that gives access to value-added α-stereogenic carboxylic acids in atom- step-economic manner is highly attractive. However, it has remained a formidable challenge for the synthetic community. Here, first example Cu-catalyzed regio- enantioselective boracarboxylation reaction on various arylalkenes diboron under atmospheric pressure CO2 described, which afforded variety chiral β-boron-functionalized α-aryl up 87% yield 97% ee mild conditions. Importantly, α-substituted could also be subject this protocol excellent enantiopurities, thereby rendering efficient approach generation enantioenriched α-chiral all-carbon quaternary center. Moreover, high functional group tolerance, scalable synthesis, facile bioactive compounds, like (−)-scopolamine, (−)-anisodamine, (−)-tropicamide, further demonstrated utility strategy.

Language: Английский

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Activation of the Si–B interelement bond related to catalysis

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(3), P. 2010 - 2073

Published: Dec. 16, 2020

Covering the past seven years, this review comprehensively summarises latest progress in preparation and application of Si–B reagents, including discussion relevant reaction mechanisms.

Language: Английский

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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

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Catalytic asymmetric synthesis of monofluoroalkenes and gem-difluoroalkenes: advances and perspectives

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(10), P. 2315 - 2327

Published: Jan. 1, 2021

The latest achievements in the catalytic asymmetric synthesis of both monofluoro- and gem-difluoroalkenes are discussed.

Language: Английский

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Reductive quenching-initiated catalyst-controlled divergent alkylation of α-CF3-olefins

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(6), P. 1380 - 1393

Published: April 21, 2022

Gem-difluoroalkenes and trifluoromethyl alkanes are pervasive in biologically active molecules. Photo-catalyzed alkylation of α-CF3-olefins provides a straightforward approach to access these scaffolds; however, such strategy is often hampered, gem-difluoroalkenes usually formed instead under reductive quenching-initiated photoredox conditions. It both mechanistically synthetically appealing if simple change the catalyst can chemo-selectively lead either type products. Here, we show visible-light-induced photo-catalyst for preparing from α-CF3-olefins. The chemo-selectivity reactions arises judicious choice rather than modification substrate structures. A wide variety substrates bearing an assortment functional groups (62 examples) compatible with this strategy. use HFIP as additive promotes formation probably via facilitation hydrogen atom transfer step O-H but not α-C-H bond.

Language: Английский

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