Copper-Catalyzed Borylative Difunctionalization of π-Systems

ACS Catalysis, Год журнала: 2020, Номер 10(19), С. 11578 - 11622

Опубликована: Авг. 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.

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 2919 - 2927

Опубликована: Янв. 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.

Язык: Английский

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Copper-catalyzed functionalization of enynes

Chemical Science, Год журнала: 2020, Номер 11(42), С. 11380 - 11393

Опубликована: Янв. 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.

Язык: Английский

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Activation of the Si–B interelement bond related to catalysis

Chemical Society Reviews, Год журнала: 2020, Номер 50(3), С. 2010 - 2073

Опубликована: Дек. 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.

Язык: Английский

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Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(49), С. 20818 - 20827

Опубликована: Дек. 6, 2021

Multicomponent reactions that involve interception of onium ylides through Aldol, Mannich, and Michael addition with corresponding bench-stable acceptors have demonstrated broad applications in synthetic chemistry. However, because the high reactivity transient survival these situ generated intermediates, substitution-type process, especially asymmetric catalytic version, remains hitherto unknown. Herein, a three-component allylation α-diazo carbonyl compounds alcohols allyl carbonates is disclosed by employing ternary cooperative catalysis achiral Pd-complex, Rh2(OAc)4, chiral phosphoric acid CPA. This method represents first example allylic alkylation an SN1-type trapping which involves convergent assembly two active Pd-allyl species, enol derived from ylides, providing expeditious access to α,α-disubstituted ketones good yields excellent enantioselectivity. Combined experimental computational studies shed light on mechanism this novel reaction, including critical role Xantphos ligand origin

Язык: Английский

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Copper-Catalyzed Enantiotopic-Group-Selective Allylation of gem-Diborylalkanes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(2), С. 1069 - 1077

Опубликована: Янв. 4, 2021

We report a copper-catalyzed enatiotopic-group-selective allylation of gem-diborylalkanes with allyl bromides. The combination copper(I) bromide and H8-BINOL derived phosphoramidite ligand proved to be the most effective catalytic system provide various enantioenriched homoallylic boronate esters, containing boron-substituted stereogenic center that is solely from gem-diborylalkanes, in good yields high enantiomeric ratios under mild conditions. Experimental theoretical studies have been conducted elucidate reaction mechanism, revealing how transmetalation chiral copper complex occurs generate α-borylalkyl-copper species for first time. Additional synthetic applications synthesis building blocks are also included.

Язык: Английский

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Copper-Catalyzed Yne-Allylic Substitutions Using Stabilized Nucleophiles

ACS Catalysis, Год журнала: 2022, Номер 12(12), С. 6840 - 6850

Опубликована: Май 25, 2022

Using stabilized "soft" nucleophiles in copper-catalyzed allylic substitutions is highly desirable but remains an unsolved challenge for the last 40 years. In this work, a general protocol of using such as indoles, pyrroles, amines, and 1,3-dicarbonyls has been developed, delivering large variety functionalized 1,3- 1,4-enynes with high levels regio- stereoselectivities (67 examples). A range further transformations products can be easily achieved to release various molecules. mechanistic rationale copper acetylide-bonded cation key intermediate that features outer-sphere nucleophilic attack proposed. Additionally, series diversified reactivities have demonstrated, which will inspire studies.

Язык: Английский

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Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp³)–O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(8), С. 4613 - 4625

Опубликована: Фев. 20, 2023

Since C(sp3)–O bonds are a ubiquitous chemical motif in both natural and artificial organic molecules, the universal transformation of will be key technology for achieving carbon neutrality. We report herein that gold nanoparticles supported on amphoteric metal oxides, namely, ZrO2, efficiently generated alkyl radicals via homolysis unactivated bonds, which consequently promoted C(sp3)–Si bond formation to give diverse organosilicon compounds. A wide array esters ethers, either commercially available or easily synthesized from alcohols participated heterogeneous gold-catalyzed silylation by disilanes alkyl-, allyl-, benzyl-, allenyl silanes high yields. In addition, this novel reaction could applied upcycling polyesters, i.e., degradation polyesters synthesis organosilanes were realized concurrently unique catalysis nanoparticles. Mechanistic studies corroborated notion generation is involved coupling cooperation an acid–base pair ZrO2 responsible stable bonds. The reusability air tolerance catalysts as well simple, scalable, green system enabled practical

Язык: Английский

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Copper-Catalyzed General and Selective α-C(sp³)–H Silylation of Amides via 1,5-Hydrogen Atom Transfer

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1725 - 1732

Опубликована: Янв. 18, 2024

The development of a general and selective method for α-C(sp3)–H silylation feedstock amines has been long-standing challenge. In this paper, we disclose mild, general, practical, highly regio- diastereoselective various readily available acyclic, cyclic, aromatic with silylboranes through copper-catalyzed intramolecular 1,5-hydrogen atom transfer (HAT) strategy. mild activation 2-iodobenzamide to generate an aryl radical enabled by ligand-coordinated silyl copper complex without additional heating or photoinduced conditions, as well the 1,5-HAT process produce crucial α-aminoalkyl species, is key success chemistry. This protocol demonstrated its potential utility in late-stage modification structurally drugs bioactive molecules. Therefore, it expected that will find applications synthetic chemistry drug discovery.

Язык: Английский

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The role of silicon in drug discovery: a review

RSC Medicinal Chemistry, Год журнала: 2024, Номер 15(10), С. 3286 - 3344

Опубликована: Янв. 1, 2024

This review aims to highlight the role of silicon in drug discovery.

Язык: Английский

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