scholarly journals Nickel-Catalyzed Reductive Coupling of Unactivated Alkyl Bromides and Aliphatic Aldehydes

2021 ◽  
Author(s):  
Cole Cruz ◽  
John Montgomery
Keyword(s):  
Functional Groups ◽  
Catalytic System ◽  
Cross Coupling ◽  
Secondary Alcohols ◽  
Reductive Coupling ◽  
Aliphatic Aldehydes ◽  
Alkyl Bromide ◽  
Alkyl Bromides ◽  
Wide Range ◽  
Ni Species

We report the development of a mild, convenient coupling of aliphatic aldehydes and unactivated alkyl bromides. The catalytic system features the use of a common Ni(II) precatalyst and a readily available bisoxazoline ligand and affords silyl-protected secondary alcohols. The reaction is operationally simple, utilizing Mn as a stoichiometric reductant, and tolerates a wide range of functional groups. Initial mechanistic experiments support a mechanism featuring an alpha-silyloxy Ni species which undergoes formal oxidative addition of the alkyl bromide species via a reductive cross-coupling pathway.

scholarly journals Nickel-Catalyzed Reductive Coupling of Unactivated Alkyl Bromides and Aliphatic Aldehydes

2021 ◽  
Author(s):  
Cole Cruz ◽  
John Montgomery
Keyword(s):  
Functional Groups ◽  
Catalytic System ◽  
Cross Coupling ◽  
Secondary Alcohols ◽  
Reductive Coupling ◽  
Aliphatic Aldehydes ◽  
Alkyl Bromide ◽  
Alkyl Bromides ◽  
Wide Range ◽  
Ni Species

We report the development of a mild, convenient coupling of aliphatic aldehydes and unactivated alkyl bromides. The catalytic system features the use of a common Ni(II) precatalyst and a readily available bisoxazoline ligand and affords silyl-protected secondary alcohols. The reaction is operationally simple, utilizing Mn as a stoichiometric reductant, and tolerates a wide range of functional groups. Initial mechanistic experiments support a mechanism featuring an alpha-silyloxy Ni species which undergoes formal oxidative addition of the alkyl bromide species via a reductive cross-coupling pathway.

scholarly journals Nickel-catalyzed reductive coupling of homoenolates and their higher homologues with unactivated alkyl bromides

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Tingzhi Lin ◽  
Yuanyun Gu ◽  
Pengcheng Qian ◽  
Haixing Guan ◽  
Patrick J. Walsh ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Transition Metal ◽  
Functional Groups ◽  
Oxidative Addition ◽  
Cross Coupling ◽  
Single Electron Transfer ◽  
Reductive Coupling ◽  
Mechanistic Studies ◽  
Alkyl Bromide ◽  
Alkyl Bromides

Abstract The catalytic generation of homoenolates and their higher homologues has been a long-standing challenge. Like the generation of transition metal enolates, which have been used to great affect in synthesis and medicinal chemistries, homoenolates and their higher homologues have much potential, albeit largely unrealized. Herein, a nickel-catalyzed generation of homoenolates, and their higher homologues, via decarbonylation of readily available cyclic anhydrides has been developed. The utility of nickel-bound homoenolates and their higher homologues is demonstrated by cross-coupling with unactivated alkyl bromides, generating a diverse array of aliphatic acids. A broad range of functional groups is tolerated. Preliminary mechanistic studies demonstrate that: (1) oxidative addition of anhydrides by the catalyst is faster than oxidative addition of alkyl bromides; (2) nickel bound metallocycles are involved in this transformation and (3) the catalyst undergoes a single electron transfer (SET) process with the alkyl bromide.

scholarly journals Nickel-Catalyzed Reductive Coupling of Unactivated Alkyl Bromides and Aliphatic Aldehydes

2021 ◽  
Author(s):  
Cole L. Cruz ◽  
John Montgomery
Keyword(s):  
Catalytic System ◽  
Reductive Coupling ◽  
Aliphatic Aldehydes ◽  
Alkyl Bromides

A mild, convenient coupling of aliphatic aldehydes and unactivated alkyl bromides has been developed. The catalytic system features the use of a common Ni(II) precatalyst and a readily available bioxazoline...

Ether Synthesis through Reductive Cross-Coupling of Ketones with Alcohols Using Me2SiHCl as both Reductant and Lewis Acid

Synlett ◽  
2017 ◽  
Vol 28 (18) ◽  
pp. 2425-2428 ◽  
Author(s):  
Bill Morandi ◽  
Yong Lee
Keyword(s):  
Functional Groups ◽  
Lewis Acid ◽  
Carbonyl Compounds ◽  
Cross Coupling ◽  
Wide Range ◽  
Direct Cross ◽  
Sterically Hindered ◽  
Polar Functional Groups ◽  
Ether Synthesis ◽  
Dialkyl Ethers

We report that a Lewis acidic silane, Me2SiHCl, can mediate the direct cross-coupling of a wide range of carbonyl compounds with alcohols to form dialkyl ethers. The reaction is operationally simple, tolerates a range of polar functional groups, can be utilized to make sterically hindered ethers, and is extendable to sulfur and nitrogen nucleo­philes.

scholarly journals Bis-NHC–Ag/Pd(OAc)2 Catalytic System Catalyzed Transfer Hydrogenation Reaction

Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 8
Author(s):  
Hui-Ju Chen ◽  
Chien-Cheng Chiu ◽  
Tsui Wang ◽  
Dong-Sheng Lee ◽  
Ta-Jung Lu
Keyword(s):  
Functional Groups ◽  
Catalytic System ◽  
High Efficiency ◽  
Aqueous Media ◽  
Hydrogenation Reaction ◽  
Transfer Hydrogenation ◽  
Terminal Alkynes ◽  
Wide Range ◽  
Transfer Hydrogenation Reaction

The bis-NHC–Ag/Pd(OAc)2 catalytic system (NHC = N-heterocyclic carbene), a combination of bis-NHC–Ag complex and Pd(OAc)2, was found to be a smart catalyst in the Pd-catalyzed transfer hydrogenation of various functionalized arenes and internal/terminal alkynes. The catalytic system demonstrated high efficiency for the reduction of a wide range of various functional groups such as carbonyls, alkynes, olefins, and nitro groups in good to excellent yields and high chemoselectivity for the reduction of functional groups. In addition, the protocol was successfully exploited to stereoselectivity for the transformation of alkynes to alkenes in aqueous media under air. This methodology successfully provided an alternative useful protocol for reducing various functional groups and a simple operational protocol for transfer hydrogenation.

Electrochemical Synthesis of 2-Hydroxy-para-terphenyls by Dehydrogenative Anodic C–C Cross-Coupling Reaction

Synlett ◽  
2019 ◽  
Vol 30 (10) ◽  
pp. 1174-1177 ◽  
Author(s):  
Sebastian Lips ◽  
Robert Franke ◽  
Siegfried R. Waldvogel
Keyword(s):  
Functional Groups ◽  
Electrochemical Synthesis ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Cross Coupling Reaction ◽  
Wide Range ◽  
Broad Variety ◽  
First Time ◽  
Fast Access

The anodic C–C cross-coupling reaction provides fast access to a wide range of bi- and terarylic scaffolds by electrochemically mediated arylation reactions. Herein, a metal- and reagent-free electrosynthetic protocol for the synthesis of nonsymmetrical 2-hydroxy-para-teraryl derivatives is presented for the first time. It is scalable, easy to conduct, and allows the use of a broad variety of different functional groups.

scholarly journals A New Efficient Catalytic System for the Chemoselective Cobalt-Catalyzed Cross-Coupling of Aryl Grignard Reagents with Primary and Secondary Alkyl Bromides

2009 ◽  
Vol 11 (7) ◽  
pp. 1671-1671
Author(s):  
Gérard Cahiez ◽  
Christophe Chaboche ◽  
Christophe Duplais ◽  
Alban Moyeux
Keyword(s):  
Catalytic System ◽  
Cross Coupling ◽  
Grignard Reagents ◽  
Alkyl Bromides

scholarly journals A New Efficient Catalytic System for the Chemoselective Cobalt-Catalyzed Cross-Coupling of Aryl Grignard Reagents with Primary and Secondary Alkyl Bromides

2009 ◽  
Vol 11 (2) ◽  
pp. 277-280 ◽  
Author(s):  
Gérard Cahiez ◽  
Christophe Chaboche ◽  
Christophe Duplais ◽  
Alban Moyeux
Keyword(s):  
Catalytic System ◽  
Cross Coupling ◽  
Grignard Reagents ◽  
Alkyl Bromides

scholarly journals Ni-catalyzed deaminative cross-electrophile coupling of Katritzky salts with halides via C─N bond activation

2019 ◽  
Vol 5 (6) ◽  
pp. eaaw9516 ◽  
Author(s):  
Shengyang Ni ◽  
Chun-Xiao Li ◽  
Yu Mao ◽  
Jianlin Han ◽  
Yi Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Primary Amines ◽  
One Pot ◽  
Carbon Centers ◽  
Alkyl Bromides ◽  
Wide Range ◽  
Coupling Strategy ◽  
The One

The reductive cross-coupling of sp3-hybridized carbon centers represents great synthetic values and insurmountable challenges. In this work, we report a nickel-catalyzed deaminative cross-electrophile coupling reaction to construct C(sp)─C(sp3), C(sp2)─C(sp3), and C(sp3)─C(sp3) bonds. A wide range of coupling partners including aryl iodides, bromoalkynes, or alkyl bromides are stitched with alkylpyridinium salts that derived from the corresponding primary amines. The advantages of this methodology are showcased in the two-step synthesis of the key lactonic moiety of (+)-compactin and (+)-mevinolin. The one-pot procedure without isolation of alkylpyridinium tetrafluoroborate salt is also proven to be successful. This cross-coupling strategy of two electrophiles provides a highly valuable vista for the convenient installation of alkyl substituents and late functionalizations of sp3 carbons.

Efficient Synthesis of Diaryl Sulfides by Copper-catalysed Coupling of Aryl Halides and Thioacetate in Water

2013 ◽  
Vol 37 (1) ◽  
pp. 19-21 ◽  
Author(s):  
Yimin Zhang ◽  
Iiu ◽  
Junmin Chen
Keyword(s):  
Functional Groups ◽  
Catalytic System ◽  
Aryl Halides ◽  
Efficient Synthesis ◽  
Highly Efficient ◽  
Wide Range ◽  
High Yields

A simple economical, and highly efficient catalytic system for the synthesis of diaryl sulfides by a copper-catalysed coupling of aryl halides and thioacetate in water has been developed. A variety of aryl halides reacted with thioacetate to give the desired products in high yields up to 95%. The present catalysis protocol tolerated a wide range of functional groups, including amino, fluoro, and carboxyl moieties.

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