Ni-Catalyzed dehydrogenative coupling of primary and secondary alcohols with methyl-<i>N</i>-heteroaromatics

Rana, Jagannath; Babu, Reshma; Subaramanian, Murugan; Balaraman, Ekambaram

doi:10.1039/c8qo00764k

Cited by 49 publications

(12 citation statements)

References 81 publications

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“…Of late, in 2018, the first base-metal reports on nickel catalyzed direct C(sp 3 )-alkylation of methyl-Nheteroaromatics using primary and secondary alcohols was reported by our group. [20] The use of commercially available nickel salt as a catalyst provides the diverse methyl-Nheteroaromatic derivatives via the dehydrogenative coupling pathway and releases water as the sole by-product (Scheme 8).…”

Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

First‐Row Transition‐Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account

Subaramanian

Sivakumar

Balaraman

2021

The Chemical Record

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The development of sustainable catalytic protocols that circumvent the use of expensive and precious metal catalysts and avoid toxic reagents plays a crucial role in organic synthesis. Indeed, the direct employment of simple and abundantly available feedstock chemicals as the starting materials broadens their synthetic application in contemporary research. In particular, the transition metal-catalyzed diversification of alcohols with various nucleophilic partners to construct a wide range of building blocks is a powerful and highly desirable methodology. Moreover, the replacement of precious metal catalysts by non-precious and less toxic metals for selective transformations is one of the main goals and has been paid significant attention to in modern chemistry. In view of this, the first-row transition metal catalysts find extensive applications in various synthetic transformations such as catalytic hydrogenation, dehydrogenation, and related reactions. Herein, we have disclosed our recent developments on the base-metal catalysis such as Mn, Fe, Co, and Ni for the acceptorless dehydrogenation reactions and its application in the CÀ C and CÀ N bond formation via hydrogen auto-transfer (HA) and acceptorless dehydrogenation coupling (ADC) reactions. These HA/ADC protocols employ alcohol as alkylating agents and eliminate water and/or hydrogen gas as by-products, representing highly atom-efficient and environmentally benign reactions. Furthermore, diverse simple to complex organic molecules synthesis by CÀ C and CÀ N bond formation using feedstock alcohols are also overviewed. Overall, this account deals with the contribution and development of efficient and novel homogeneous as well as heterogeneous base-metal catalysts for sustainable chemical synthesis.

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Section: P E R S O N a L A C C O U N T T H E C H E M I C A L R E C O R Dmentioning

confidence: 99%

First‐Row Transition‐Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account

Subaramanian

Sivakumar

Balaraman

2021

The Chemical Record

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“…For example, Rana and co-workers reported the dehydrogenative coupling of primary and secondary alcohols with Methyl-N-Heteroaromatics catalyzed by in situ generated Ni-N,N,N',N'tetramethylethylenediamine (TMEDA) complex (Scheme 14). [27] Scheme 12. Proposed mechanism of α-alkylation of nitriles.…”

Section: Biaryl Ligandsmentioning

confidence: 99%

Recent Developments in Dehydrogenative Organic Transformations Catalyzed by Homogeneous Phosphine‐Free Earth‐Abundant Metal Complexes

et al. 2021

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Stoichiometric amounts of various oxidants have long been employed for the oxidation of organic compounds. The major drawback of this method is the amount of toxic waste produced, which is in sharp contrast to principles of green chemistry. In catalytic dehydrogenation pathways, hydrogen carrier organic compounds (HCOCs) containing O−H, C−H, and N−H bonds can be transformed to their oxidized forms by removing two hydrogen atoms from the starting materials. Among the homogeneous transition metal‐ligand complexes that have been applied in a catalytic dehydrogenative approach, phosphine ligands have frequently been used. Over the past decades, phosphine‐free ligand systems have since been developed and implemented in various organic reactions to overcome the drawbacks associated with phosphine‐based catalysts. The aim of this review is to summarize the use of non‐phosphinic ligand‐metal complexes in organic transformations proceeding by a dehydrogenative pathway.

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“…Likewise, the C(sp 3 )–H bond (functionalization) alkylations of N ‐heteroaromatics using alcohol with transition‐metal (Ru, Ir) is reported by Kempe et al [ 41 ] Obora and co‐workers reported iridium catalyzed α‐alkylation of 2‐methyl‐ N ‐heteroaromatics with alcohols. [ 42 ] Shimizu and co‐workers reported Pt‐supported heterogeneous catalysis, [ 43 ] Lang and co‐workers utilized the ligand‐free RuCl 3 catalysis, [ 44 ] Banerjee and co‐workers, [ 45 ] Balaraman and co‐workers [ 46 ] reported Ni‐Catalyzed dehydrogenative coupling of secondary and primary alcohols with methyl‐ N ‐heteroaromatics.…”

Section: Introductionmentioning

confidence: 99%

Cu‐TEMPO Catalyzed Dehydrogenative Friedlander Annulation/sp³ C–H Functionalization/Spiroannulation towards Spiro[indoline‐3,3'‐pyrrolizin]‐2'‐yl)‐4‐phenylquinoline‐3‐Carboxylates

2020

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A series of spiro[indoline‐3,3'‐pyrrolizin]‐2'‐yl)‐4‐phenylquinoline‐3‐carboxylate 6 from 2‐amino‐5‐chlorobenzhydrol 1, benzyl alcohols 3, and methyl or ethyl acetoacetate 2 is reported by the Cu(OAc)2, TEMPO catalyzed dehydrogenative Friedlander annulation/sp3–CH‐functionalization/regioselective 1,3‐ dipolar cyclo‐ addition. Likewise, chimanine A analogues 7 were obtained using a similar strategy in DES (Deep Eutectic Solvents) as a reaction medium in excellent yields.

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Ni-Catalyzed dehydrogenative coupling of primary and secondary alcohols with methyl-N-heteroaromatics

Abstract: Here we report the first base-metal catalyzed dehydrogenative coupling of primary (aromatic, heteroaromatic, and aliphatic) and secondary alcohols with methyl-N-heteroaromatics to form various C(sp3)-alkylated N-heteroaromatics.

Cited by 49 publications

References 81 publications

First‐Row Transition‐Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account

First‐Row Transition‐Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account

Recent Developments in Dehydrogenative Organic Transformations Catalyzed by Homogeneous Phosphine‐Free Earth‐Abundant Metal Complexes

Cu‐TEMPO Catalyzed Dehydrogenative Friedlander Annulation/sp³ C–H Functionalization/Spiroannulation towards Spiro[indoline‐3,3'‐pyrrolizin]‐2'‐yl)‐4‐phenylquinoline‐3‐Carboxylates

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Ni-Catalyzed dehydrogenative coupling of primary and secondary alcohols with methyl-N-heteroaromatics

Abstract: Here we report the first base-metal catalyzed dehydrogenative coupling of primary (aromatic, heteroaromatic, and aliphatic) and secondary alcohols with methyl-N-heteroaromatics to form various C(sp3)-alkylated N-heteroaromatics.

Cited by 49 publications

References 81 publications

First‐Row Transition‐Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account

First‐Row Transition‐Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account

Recent Developments in Dehydrogenative Organic Transformations Catalyzed by Homogeneous Phosphine‐Free Earth‐Abundant Metal Complexes

Cu‐TEMPO Catalyzed Dehydrogenative Friedlander Annulation/sp3 C–H Functionalization/Spiroannulation towards Spiro[indoline‐3,3'‐pyrrolizin]‐2'‐yl)‐4‐phenylquinoline‐3‐Carboxylates

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Cu‐TEMPO Catalyzed Dehydrogenative Friedlander Annulation/sp³ C–H Functionalization/Spiroannulation towards Spiro[indoline‐3,3'‐pyrrolizin]‐2'‐yl)‐4‐phenylquinoline‐3‐Carboxylates