Pincer‐Type Ligand‐Assisted Catalysis and Small‐Molecule Activation by non‐VSEPR Main‐Group Compounds DOI
Subrata Kundu

Chemistry - An Asian Journal, Journal Year: 2020, Volume and Issue: 15(20), P. 3209 - 3224

Published: Aug. 14, 2020

In 2005, a facile dihydrogen activation was reported by the Power group using an alkyne analog of germanium [ArGe≡GeAr; Ar=2,6-Trip2 -C6 H3 (Trip=2,4,6-i Pr3 H2 )]. After that, significant progress has been made in various small molecules main-group compounds, and variety stoichiometric catalytic processes have formulated p-block elements. this regard, compounds containing low-valent elements with frontier orbitals relatively energy gaps or forming frustrated Lewis pair (FLP) became quite successful. spite these promising transformations, redox-cycling catalysts based on remain extremely rare. Recently, it observed that pincer type ligands supported geometry constrained are capable acting as redox similar to those transition metals. review, we focus synthesis structural aspects ligands. Emphasis placed their applications activity activation.

Language: Английский

Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis DOI
Nicholas E. S. Tay, Dan Lehnherr, Tomislav Rovis

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2487 - 2649

Published: Nov. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Language: Английский

Citations

357
Single-atom logic for heterocycle editing DOI
Justin Jurczyk, Jisoo Woo, Sojung F. Kim

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(5), P. 352 - 364

Published: April 11, 2022

Language: Английский

Citations

280
Phosphorus-Based Catalysis DOI Creative Commons
Changmin Xie, Andrew J. Smaligo,

Xian-Rong Song

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(4), P. 536 - 558

Published: March 16, 2021

Phosphorus-based organocatalysis encompasses several subfields that have undergone rapid growth in recent years. This Outlook gives an overview of its various aspects. In particular, we highlight key advances three topics: nucleophilic phosphine catalysis, organophosphorus catalysis to bypass oxide waste, and compound-mediated single electron transfer processes. We briefly summarize five additional chiral phosphoric acid Lewis base iminophosphorane super phosphonium salt phase frustrated pair catalysis. Although it is not catalytic nature, also discuss novel discoveries are emerging phosphorus(V) ligand coupling. conclude with some ideas about the future

Language: Английский

Citations

236
Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15 DOI
Jeffrey M. Lipshultz, Gen Li, Alexander T. Radosevich

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(4), P. 1699 - 1721

Published: Jan. 19, 2021

A growing number of organopnictogen redox catalytic methods have emerged-especially within the past 10 years-that leverage plentiful reversible two-electron chemistry Group 15. The goal this Perspective is to provide readers context understand dramatic developments in catalysis over decade with an eye toward future development. An exposition fundamental differences atomic structure and bonding pnictogens, thus molecular electronic compounds, presented establish backdrop against which reactivity-and ultimately catalysis-is framed. deep appreciation these underlying periodic principles informs understanding differing modes evokes key challenges field moving forward. We close by addressing forward-looking directions likely animate area years come. What new manifolds can be developed through creative catalyst reaction design that take advantage intrinsic reactivity pnictogens drive discoveries catalysis?

Language: Английский

Citations

219
Synthesis of polysubstituted azepanes by dearomative ring expansion of nitroarenes DOI
Rory C. Mykura, Raquel Sánchez-Bento, Esteban Matador

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(5), P. 771 - 779

Published: Jan. 25, 2024

Language: Английский

Citations

39
Light‐Promoted C–N Coupling of Aryl Halides with Nitroarenes DOI
Gang Li, Liu Yang,

Jianjun Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5230 - 5234

Published: Nov. 13, 2020

Abstract A photochemical C–N coupling of aryl halides with nitroarenes is demonstrated for the first time. Catalyzed by a Ni II complex in absence any external photosensitizer, readily available undergo variety halides, providing step‐economic extension to widely used Buchwald–Hartwig reaction. The method tolerates partners steric‐congestion and functional groups sensitive bases nucleophiles. Mechanistic studies suggest that reaction proceeds via addition an radical, generated from I /Ni III cycle, nitrosoarene intermediate.

Language: Английский

Citations

113
Site-specific Umpolung amidation of carboxylic acids via triplet synergistic catalysis DOI Creative Commons

Yunyun Ning,

Shuaishuai Wang,

Muzi Li

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: July 30, 2021

Abstract Development of catalytic amide bond-forming methods is important because they could potentially address the existing limitations classical using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction carboxylic acids with nitroarenes and nitroalkanes enabled by triplet synergistic catalysis FeI 2 , P(V)/P(III) photoredox catalysis, which avoids production byproducts from stoichiometric coupling A wide range acids, including aliphatic, aromatic alkenyl participate smoothly in such reactions, generating structurally diverse amides good yields (86 examples, up to 97% yield). This strategy opens a method challenging regioselectivity issues between nucleophilic functional groups, complements group compatibility protocols. The synthetic robustness demonstrated late-stage modification complex molecules gram-scale applications.

Language: Английский

Citations

77
Decarboxylative tandem C-N coupling with nitroarenes via SH2 mechanism DOI Creative Commons

Shuaishuai Wang,

Tingrui Li,

Chengyihan Gu

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 4, 2022

Abstract Aromatic tertiary amines are one of the most important classes organic compounds in chemistry and drug discovery. It is difficult to efficiently construct from primary via classical nucleophilic substitution due consecutive overalkylation. In this paper, we have developed a radical tandem C-N coupling strategy aromatic commercially available carboxylic acids nitroarenes. A variety can be furnished good yields (up 98%) with excellent functional group compatibility under mild reaction conditions. The use two different also allows for concise synthesis nonsymmetric satisfactory yields. Mechanistic studies suggest intermediacy arylamine–(TPP)Fe(III) species might provide possible evidence an S H 2 (bimolecular homolytic substitution) pathway critical bond formation step.

Language: Английский

Citations

52
Tandem C/N-Difunctionalization of Nitroarenes: Reductive Amination and Annulation by a Ring Expansion/Contraction Sequence DOI
Gen Li, Marissa N. Lavagnino, Siraj Z. Ali

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(1), P. 41 - 46

Published: Dec. 23, 2022

A synthetic method for the reductive transformation of nitroarenes into ortho-aminated and -annulated products is reported. The operates via exhaustive deoxygenation by an organophosphorus catalyst a mild terminal reductant to access aryl nitrenes, which after ring expansion, are trapped amine nucleophiles give dearomatized 2-amino-3H-azepines. Treatment these ring-expanded intermediates with acyl electrophiles triggers 6π electrocyclization extrude nitrogen atom restore aromaticity phenyl ring, delivers C–H functionalization 2-aminoanilide benzimidazole products.

Language: Английский

Citations

46
Expanding Reaction Profile of Allyl Carboxylates via 1,2-Radical Migration (RaM): Visible-Light-Induced Phosphine-Catalyzed 1,3-Carbobromination of Allyl Carboxylates DOI
Gaoyuan Zhao, Sang-Hyun Lim, Djamaladdin G. Musaev

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8275 - 8284

Published: April 5, 2023

Allyl carboxylates are useful synthetic intermediates in a variety of organic transformations, including catalytic nucleophilic/electrophilic allylic substitution reactions and 1,2-difunctionalization reactions. However, the 1,3-difunctionalization allyl remains elusive. Herein, we report first photoinduced, phosphine-catalyzed 1,3-carbobromination carboxylates, affording range valuable substituted isopropyl (sIPC). The transformation has broad functional group tolerance, is amenable to late-stage modification complex molecules gram-scale synthesis, expands reaction profiles phosphine catalysis. Preliminary experimental computational studies suggest non-chain-radical mechanism involving formation an electron donor-acceptor complex, 1,2-radical migration (RaM), Br-atom transfer processes. We anticipate that 1,2-RaM reactivity radical will both serve as platform for development new transformations synthesis.

Language: Английский

Citations

29