Picolinate-Directed Arene <i>meta</i>-C–H Amination via FeCl<sub>3</sub> Catalysis

Anugu, Raghunath Reddy; Munnuri, Sailu; Falck, John R.

doi:10.1021/jacs.9b13753

Cited by 55 publications

(28 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although C–H functionalization has emerged as a promising strategy that maximizes atom- and step-economy, state-of-the-art methods for amine synthesis typically provide N -protected or N -substituted products that require additional manipulation to access the corresponding primary amines . Recently, a few methods have been developed for primary amination of C(sp 2 )–H bonds, including photoredox catalysis, electrochemical catalysis, and the use of other novel amination reagents and metal catalysts . Primary amination of C(sp 3 )–H bonds, however, has remained elusive.…”

mentioning

confidence: 99%

Enzymatic Primary Amination of Benzylic and Allylic C(sp³)–H Bonds

2020

View full text Add to dashboard Cite

Aliphatic primary amines are prevalent in natural products, pharmaceuticals, and functional materials. While a plethora of processes are reported for their synthesis, methods that directly install a free amine group into C(sp3)–H bonds remain unprecedented. Here, we report a set of new-to-nature enzymes that catalyze the direct primary amination of C(sp3)–H bonds with excellent chemo-, regio-, and enantioselectivity, using a readily available hydroxylamine derivative as the nitrogen source. Directed evolution of genetically encoded cytochrome P411 enzymes (P450s whose Cys axial ligand to the heme iron has been replaced with Ser) generated variants that selectively functionalize benzylic and allylic C–H bonds, affording a broad scope of enantioenriched primary amines. This biocatalytic process is efficient and selective (up to 3930 TTN and 96% ee), and can be performed on preparative scale.

show abstract

mentioning

confidence: 99%

Enzymatic Primary Amination of Benzylic and Allylic C(sp³)–H Bonds

2020

View full text Add to dashboard Cite

show abstract

“…[41][42][43][44][45][46][47][48][49][50][51][52][53] Recently, we discovered dioxazolones can undergo intermolecular N-N coupling with arylamines to make hydrazides under either iridium or iron catalysis. [54][55][56][57][58][59][60][61][62][63][64] Mechanistic studies of the Ir-catalyzed system indicated an outer-sphere nucleophilic attack of the nitrogen group of Ir-nitrenoid intermediate by amine leads to the N-N coupling product.…”

Section: Resultsmentioning

confidence: 99%

Nitrene-Mediated P–N Coupling Under Iron Catalysis

et al. 2022

View full text Add to dashboard Cite

P-N and P=N bonds play important roles in the design and synthesis of functional molecules such as bioactive compounds and organic ligands for catalysis. Existing methods for P-N coupling mostly rely on Staudinger condensation or nucleophilic substitution between phosphorus electrophiles and amine nucleophiles. Herein, we report a nitrene-mediated intermolecular P-N coupling reaction between various phosphorus nucleophiles and dioxazolones under simple iron-catalyzed conditions. These reactions offer an efficient, versatile, and broadly applicable method for synthesis of a range of N-P compounds including amidophosphines, iminophosphonamides, phosphinamides, aminophosphines, and iminophosphoranes from readily available precursors under mild conditions.

show abstract

“…In this regard, while representing the advances of DGs, Anugu et al has provided a simple yet powerful strategy for meta-CÀ H amination of arenes in the presence of picolinate as a key DG (Scheme 34). [141] They have utilized this sustainable, cost-effective, and operationally easy methodology to late-stage transforms for many polyfunctional molecules involving FeCl 3 and HOSA (hydroxylamine-Osulfonic acid) in the presence of triethylamine.…”

Section: Meta-cà H Amination Through Picolinate As a Vital Directing mentioning

confidence: 99%

Recent Developments in Remote Meta‐C−H Bond Functionalizations

Ali

Siddiqui

2021

Adv Synth Catal

View full text Add to dashboard Cite

In the past decades, there has been a dramatic increase in the developments of novel methods for the activation/functionalization of inert C−H bonds as these protocols are not only competent, reduce the waste materials in addition to the reaction time and multiple steps but also allows the reaction to be carried out in a highly regio‐specific manner under operationally simple yet effective reaction conditions. Although, in recent years, a remarkable progress has been made in the field of ortho‐and para‐C−H bonds functionalization but to our best knowledge, the distal meta‐C−H activation/functionalization is still infancy and is yet to be explore to the advanced level. Hence, we feel that there is an urgent need to aware the research community about where the field of meta‐C−H functionalization stand at present and where it might be going in near future. To this context, we strive to compile the significant achievements made in the selective meta‐C−H bonds functionalization since 2018 to till date. More interestingly, we have also displayed an overview of the earlier reports related to the meta‐C−H activation/functionalization at the beginning of this particular manuscript, and hopefully the present review article will open diverse opportunities for the advancement of both academia as well as industry.

show abstract

Picolinate-Directed Arene meta-C–H Amination via FeCl₃ Catalysis

Cited by 55 publications

References 42 publications

Enzymatic Primary Amination of Benzylic and Allylic C(sp³)–H Bonds

Enzymatic Primary Amination of Benzylic and Allylic C(sp³)–H Bonds

Nitrene-Mediated P–N Coupling Under Iron Catalysis

Recent Developments in Remote Meta‐C−H Bond Functionalizations

Contact Info

Product

Resources

About

Picolinate-Directed Arene meta-C–H Amination via FeCl3 Catalysis

Cited by 55 publications

References 42 publications

Enzymatic Primary Amination of Benzylic and Allylic C(sp3)–H Bonds

Enzymatic Primary Amination of Benzylic and Allylic C(sp3)–H Bonds

Nitrene-Mediated P–N Coupling Under Iron Catalysis

Recent Developments in Remote Meta‐C−H Bond Functionalizations

Contact Info

Product

Resources

About

Picolinate-Directed Arene meta-C–H Amination via FeCl₃ Catalysis

Enzymatic Primary Amination of Benzylic and Allylic C(sp³)–H Bonds

Enzymatic Primary Amination of Benzylic and Allylic C(sp³)–H Bonds