New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Год журнала: 2020, Номер 120(5), С. 2613 - 2692

Опубликована: Фев. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Язык: Английский

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Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

Chemical Reviews, Год журнала: 2016, Номер 117(13), С. 9163 - 9227

Опубликована: Дек. 12, 2016

The transition-metal-catalyzed addition of C–H bonds to carbonyls, imines, and related polarized π has emerged as a particularly efficient powerful approach for the construction an incredibly diverse array heteroatom-substituted products. Readily available stable inputs are typically employed, reactions often proceed with very high functional group compatibility without production waste byproducts. Additionally, many bond additions occur within cascade reaction sequences provide rapid access different heterocyclic well carbocyclic This review highlights diversity transformations that have been achieved, catalysts used, types products prepared through bonds.

Язык: Английский

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Photoredox-Catalyzed C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1925 - 2016

Опубликована: Сен. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Язык: Английский

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Site-Selective C–H Functionalization via Synergistic Use of Electrochemistry and Transition Metal Catalysis

Accounts of Chemical Research, Год журнала: 2020, Номер 53(2), С. 300 - 310

Опубликована: Янв. 15, 2020

Electrochemical synthesis of organic compounds has emerged as an attractive and environmentally benign alternative to conventional approaches for oxidation reduction that utilizes electric current instead chemical oxidants reductants. As such, many useful transformations have been developed, including the Kolbe reaction, Simons fluorination process, Monsanto adiponitrile Shono oxidation, name a few. C-H functionalization represents one most promising reaction types among electrochemical transformations, since this process avoids prefunctionalization substrates provides novel retrosynthetic disconnections. However, site-selective anodic bonds is still fundamental challenge due high potentials compared solvents common functional groups. To overcome issue, indirect electrolysis via action mediator (a redox catalyst) regularly employed, by which selectivity can be controlled following said with substrate. Since transition metal complexes easily tuned modification ligand, synergistic use electrochemistry catalysis achieve strategy. In Account, we summarize contextualize our recent efforts toward metal-catalyzed proximal suitable directing group. We developed oxygenation, acylation, alkylation, halogenation reactions in Pd(II) species oxidized Pd(III) or Pd(IV) intermediate followed reductive elimination form corresponding C-O, C-C, C-X bonds. Importantly, improved monofunctionalization achieved Pd-catalyzed C(sp3)-H oxygenation using PhI(OAc)2 oxidant. Physical separators are sometimes used prevent deposition Pd black on cathode resulting from valent species. skirted issue through development Cu-catalyzed C(sp2)-H amination n-Bu4NI cocatalyst undivided cell. addition, Ir-catalyzed vinylic acrylic acids alkynes cell, affording various substituted α-pyrones good excellent yield. More importantly, oxidants, Ag2CO3, Cu(OAc)2, PhI(OAc)2, resulted much lower yields absence electrical under otherwise identical conditions. elaborated below, progress area effective platform friendly sustainable selective transformations.

Язык: Английский

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Arene C–H functionalisation using a removable/modifiable or a traceless directing group strategy

Chemical Society Reviews, Год журнала: 2014, Номер 43(20), С. 6906 - 6919

Опубликована: Янв. 1, 2014

The use of coordinating moieties as directing groups for the functionalisation aromatic carbon-hydrogen (C-H) bonds has become an efficient strategy selective construction new carbon-carbon (C-C) and carbon-heteroatom (C-X) in arenes. However many cannot be easily removed/modified from products after C-H functionalisation, thus limiting structural diversity products. This limitation can overcome by employing removable/modifiable or traceless which attached to starting materials detached In this tutorial review, we give overview recent advances emerging field have dramatically increased synthetic applicability processes.

Язык: Английский

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