Site‐Selective C–H Bond Activation/Functionalization of Alpha‐Amino Acids and Peptide‐Like Derivatives DOI

Tobias Brandhofer,

Olga Garcı́a Mancheño

European Journal of Organic Chemistry, Год журнала: 2018, Номер 2018(44), С. 6050 - 6067

Опубликована: Июль 11, 2018

Amino acids and peptides play an important role in nature, as well organic pharmaceutical chemistry. Therefore, the easy, straightforward versatile access of biogenic unnatural derivatives is still highly demanding. This micro‐review intends to provide reader current state art on site‐selective C–H bond functionalization technology applied α‐amino peptides, focusing different positions that can successfully be addressed date. It structured two main parts implying i) α‐C–H at peptide backbone ii) modification side‐chain. Herein, metal‐catalyzed activation, oxidative functionalization, light mediated approaches, are discussed considering challenges reactivity selectivity. The great potential these transformations also depicted with derivatization macrocyclization complex leading products importance.

Язык: Английский

A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry DOI Creative Commons
Carlo Sambiagio, David Schönbauer, Rémi Blieck

и другие.

Chemical Society Reviews, Год журнала: 2018, Номер 47(17), С. 6603 - 6743

Опубликована: Янв. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Язык: Английский

Процитировано

1473

Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds DOI
Supriya Rej, Yusuke Ano, Naoto Chatani

и другие.

Chemical Reviews, Год журнала: 2020, Номер 120(3), С. 1788 - 1887

Опубликована: Янв. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Язык: Английский

Процитировано

819

New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines DOI Creative Commons
Aaron Trowbridge, Scarlett M. Walton, Matthew J. Gaunt

и другие.

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

Процитировано

704

Complementary Strategies for Directed C(sp3)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer DOI
John C. K. Chu, Tomislav Rovis

Angewandte Chemie International Edition, Год журнала: 2017, Номер 57(1), С. 62 - 101

Опубликована: Дек. 5, 2017

Abstract The functionalization of C(sp 3 )−H bonds streamlines chemical synthesis by allowing the use simple molecules and providing novel synthetic disconnections. Intensive recent efforts in development new reactions based on C−H have led to its wider adoption across a range research areas. This Review discusses strengths weaknesses three main approaches: transition‐metal‐catalyzed activation, 1, n ‐hydrogen atom transfer, carbene/nitrene for directed unactivated bonds. For each strategy, scope, reactivity different bonds, position reacting relative directing group, stereochemical outcomes are illustrated with examples literature. aim this is provide guidance inspire future area.

Язык: Английский

Процитировано

600

Toolbox for Distal C–H Bond Functionalizations in Organic Molecules DOI

Soumya Kumar Sinha,

Srimanta Guin,

Sudip Maiti

и другие.

Chemical Reviews, Год журнала: 2021, Номер 122(6), С. 5682 - 5841

Опубликована: Окт. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Язык: Английский

Процитировано

387

HFIP in Organic Synthesis DOI
Hashim F. Motiwala,

Ahlam M. Armaly,

Jackson G. Cacioppo

и другие.

Chemical Reviews, Год журнала: 2022, Номер 122(15), С. 12544 - 12747

Опубликована: Июль 17, 2022

1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability stabilize ionic species, transfer protons, and engage range of other intermolecular interactions. The use this exponentially increased the past decade become choice some areas, such as C–H functionalization chemistry. In review, following brief history HFIP an overview physical properties, literature examples reactions using or additive are presented, emphasizing effect each reaction.

Язык: Английский

Процитировано

325

Late‐Stage Peptide Diversification by Position‐Selective C−H Activation DOI
Wei Wang, Mélanie M. Lorion, Jagrut Shah

и другие.

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(45), С. 14700 - 14717

Опубликована: Июль 3, 2018

The late-stage modification of structurally complex peptides bears great potential for drug discovery, crop protection, and the pharmaceutical industry, among others. Whereas traditional approaches largely rely on prefunctionalizations, C-H activation catalysis has in recent years emerged as an increasingly powerful tool post-translational peptide modifications a step-economic manner. Herein, we summarize progress organometallic until June 2018, including position- chemoselective palladium-, ruthenium-, manganese-catalyzed processes.

Язык: Английский

Процитировано

308

Palladium-Catalyzed C(sp3)–H Bond Functionalization of Aliphatic Amines DOI Creative Commons
Chuan He, William G. Whitehurst, Matthew J. Gaunt

и другие.

Chem, Год журнала: 2019, Номер 5(5), С. 1031 - 1058

Опубликована: Фев. 1, 2019

Язык: Английский

Процитировано

236

Pd-Catalyzed γ-C(sp3)–H Arylation of Free Amines Using a Transient Directing Group DOI
Yongwei Wu, Yan‐Qiao Chen, Tao Liu

и другие.

Journal of the American Chemical Society, Год журнала: 2016, Номер 138(44), С. 14554 - 14557

Опубликована: Окт. 27, 2016

Pd(II)-catalyzed γ-C(sp3)–H arylation of primary amines is realized by using 2-hydroxynicotinaldehyde as a catalytic transient directing group. Importantly, the catalyst and group loading can be lowered to 2% 4% respectively, thus demonstrating high efficiency this newly designed Heterocyclic aryl iodides are also compatible with reaction. Furthermore, swift synthesis 1,2,3,4-tetrahydronaphthyridine derivatives accomplished

Язык: Английский

Процитировано

234

Photoinduced Nickel-Catalyzed Chemo- and Regioselective Hydroalkylation of Internal Alkynes with Ether and Amide α-Hetero C(sp3)–H Bonds DOI
Hong‐Ping Deng,

Xuanzi Fan,

Zhihui Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(38), С. 13579 - 13584

Опубликована: Сен. 1, 2017

A direct hydroalkylation of disubstituted alkynes with unfunctionalized ethers and amides was achieved in an atom-efficient additive-free manner through the synergistic combination photoredox nickel catalysis. The protocol effective a wide range internal alkynes, providing products highly selective fashion. Notably, observed regioselectivity is complementary to conventional radical addition processes. Mechanistic investigations suggest that photoexcited iridium catalyst facilitated activation via single-electron transfer.

Язык: Английский

Процитировано

231