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, Journal Year: 2018, Volume and Issue: 2018(44), P. 6050 - 6067

Published: July 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.

Language: Английский

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

et al.

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 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.

Language: Английский

Citations

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

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(3), P. 1788 - 1887

Published: Jan. 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.

Language: Английский

Citations

819

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

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(5), P. 2613 - 2692

Published: Feb. 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.

Language: Английский

Citations

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, Journal Year: 2017, Volume and Issue: 57(1), P. 62 - 101

Published: Dec. 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.

Language: Английский

Citations

600

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

Soumya Kumar Sinha,

Srimanta Guin,

Sudip Maiti

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 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.

Language: Английский

Citations

387

HFIP in Organic Synthesis DOI
Hashim F. Motiwala,

Ahlam M. Armaly,

Jackson G. Cacioppo

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(15), P. 12544 - 12747

Published: July 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.

Language: Английский

Citations

325

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

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(45), P. 14700 - 14717

Published: July 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.

Language: Английский

Citations

308

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

et al.

Chem, Journal Year: 2019, Volume and Issue: 5(5), P. 1031 - 1058

Published: Feb. 1, 2019

Language: Английский

Citations

236

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

et al.

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(44), P. 14554 - 14557

Published: Oct. 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

Language: Английский

Citations

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

et al.

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(38), P. 13579 - 13584

Published: Sept. 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.

Language: Английский

Citations

231