scholarly journals Nickel-Catalyzed 1,2-Diarylation of Simple Alkenyl Amides

2018 ◽  
Author(s):  
Joseph Derosa ◽  
Roman Kleinmans ◽  
Van Tran ◽  
Malkanthi Karunananda ◽  
Steven Wisniewski ◽  
...  
Keyword(s):  
Computational Analysis ◽  
Functional Group ◽  
Cross Coupling ◽  
Dimethyl Fumarate ◽  
Binding Mode ◽  
Wide Range ◽  
Boronic Esters ◽  
Optimized Conditions ◽  
Potential Substrate

A nickel-catalyzed conjunctive cross-coupling of simple alkenyl amides with aryl iodides and aryl boronic esters is reported. The reaction is enabled by an electron-deficient olefin (EDO) ligand, dimethyl fumarate, and delivers the desired 1,2-diarylated products with excellent regiocontrol. Under optimized conditions, a wide range of amides derived from 3-butenoic acid, 4-pentenoic acid, and allyl amine are compatible substrates. This methodology represents the first example of regiocontrolled 1,2-diarylation directed by a native amide functional group. Computational analysis sheds light on potential substrate binding mode and the role of EDO ligand in the reductive elimination step.

scholarly journals Nickel-Catalyzed 1,2-Diarylation of Simple Alkenyl Amides

2018 ◽  
Author(s):  
Joseph Derosa ◽  
Roman Kleinmans ◽  
Van Tran ◽  
Malkanthi Karunananda ◽  
Steven Wisniewski ◽  
...  
Keyword(s):  
Computational Analysis ◽  
Functional Group ◽  
Cross Coupling ◽  
Dimethyl Fumarate ◽  
Binding Mode ◽  
Wide Range ◽  
Boronic Esters ◽  
Optimized Conditions ◽  
Potential Substrate

A nickel-catalyzed conjunctive cross-coupling of simple alkenyl amides with aryl iodides and aryl boronic esters is reported. The reaction is enabled by an electron-deficient olefin (EDO) ligand, dimethyl fumarate, and delivers the desired 1,2-diarylated products with excellent regiocontrol. Under optimized conditions, a wide range of amides derived from 3-butenoic acid, 4-pentenoic acid, and allyl amine are compatible substrates. This methodology represents the first example of regiocontrolled 1,2-diarylation directed by a native amide functional group. Computational analysis sheds light on potential substrate binding mode and the role of EDO ligand in the reductive elimination step.

Directed Nickel-Catalyzed 1,2-Dialkylation of Alkenes

2018 ◽  
Author(s):  
Joseph Derosa ◽  
Vincent A. van der Puyl ◽  
Van T. Tran ◽  
Mingyu Liu ◽  
Keary Engle
Keyword(s):  
Cross Coupling ◽  
Alkyl Halides ◽  
Wide Range ◽  
Directing Group ◽  
Optimized Conditions

A nickel-catalyzed conjunctive cross-coupling of non-conjugated alkenes, alkyl halides, and alkylzinc reagents is reported. Regioselectivity is controlled by chelation of a removable bidentate 8-aminoquinoline directing group. Under optimized conditions, a wide range of 1,2-dialkylated products can be accessed in moderate to excellent yields. To the best of our knowledge, this report represents the first example of three-component 1,2-dialkylation of non-conjugated alkenes to introduce differentiated alkyl fragments.

scholarly journals Palladium-Catalyzed Cross-Coupling of Gem-Bromofluoroalkenes with Alkylboronic Acids for the Synthesis of Alkylated Monofluoroalkenes

Molecules ◽  
2020 ◽  
Vol 25 (23) ◽  
pp. 5532
Author(s):  
Laëtitia Chausset-Boissarie ◽  
Nicolas Cheval ◽  
Christian Rolando
Keyword(s):  
Organic Synthesis ◽  
Functional Group ◽  
Materials Science ◽  
Cross Coupling ◽  
High Yield ◽  
Efficient Synthesis ◽  
Mild Conditions ◽  
Wide Range ◽  
Palladium Catalyzed ◽  
Novel Strategy

Monofluoroalkenes are versatile fluorinated synthons in organic synthesis, medicinal chemistry and materials science. In light of the importance of alkyl-substituted monofluoroalkenes efficient synthesis of these moieties still represents a synthetic challenge. Herein, we described a mild and efficient methodology to obtain monofluoroalkenes through a stereospecific palladium-catalyzed alkylation of gem-bromofluoroalkenes with primary and strained secondary alkylboronic acids under mild conditions. This novel strategy gives access to a wide range of functionalized tri- and tetrasubstituted monofluoroalkenes in high yield, with good functional group tolerance, independently from the gem-bromofluoroalkenes geometry.

scholarly journals Dual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Purui Zheng ◽  
Pan Zhou ◽  
Dong Wang ◽  
Wenhao Xu ◽  
Hepan Wang ◽  
...  
Keyword(s):  
Visible Light ◽  
Ambient Temperature ◽  
Functional Group ◽  
Cross Coupling ◽  
Strong Base ◽  
Mild Conditions ◽  
Aryl Iodides ◽  
Boronic Esters

AbstractThe flourishing Ni/photoredox-catalyzed asymmetric couplings typically rely on redox-neutral reactions. In this work, we report a reductive cross-coupling of aryl iodides and α-chloroboranes under a dual catalytic regime to further enrich the metallaphotoredox chemistry. This approach proceeds under mild conditions (visible light, ambient temperature, no strong base) to access the versatile benzylic boronic esters with good functional group tolerance and excellent enantioselectivities.

Metal-free catalyzed arylsulfonylation of chloroquinoline with sodium arylsulfinates under microwave irradiation

2018 ◽  
Vol 73 (5) ◽  
pp. 295-303 ◽  
Author(s):  
Xi-Yong Li ◽  
Ya-Min Sun ◽  
Jin-Wei Yuan
Keyword(s):  
Microwave Irradiation ◽  
Functional Group ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Metal Free ◽  
Cross Coupling Reaction ◽  
Wide Range

AbstractAn efficient protocol for the synthesis of 2-arylsulfonyl quinolines has been developed via a metal-free catalyzed cross-coupling reaction of chloroquinoline with sodium arylsulfinates in moderate-to-good yields under microwave irradiation. The reactions proceed with a wide range of substrates with good functional group tolerance.

Directed Nickel-Catalyzed 1,2-Dialkylation of Alkenes

2018 ◽  
Author(s):  
Joseph Derosa ◽  
Vincent A. van der Puyl ◽  
Van T. Tran ◽  
Mingyu Liu ◽  
Keary Engle
Keyword(s):  
Cross Coupling ◽  
Alkyl Halides ◽  
Wide Range ◽  
Directing Group ◽  
Optimized Conditions

A nickel-catalyzed conjunctive cross-coupling of non-conjugated alkenes, alkyl halides, and alkylzinc reagents is reported. Regioselectivity is controlled by chelation of a removable bidentate 8-aminoquinoline directing group. Under optimized conditions, a wide range of 1,2-dialkylated products can be accessed in moderate to excellent yields. To the best of our knowledge, this report represents the first example of three-component 1,2-dialkylation of non-conjugated alkenes to introduce differentiated alkyl fragments.

scholarly journals Nickel-Catalyzed 1,2-Diarylation of Alkenyl Ketones: A Comparative Study of Carbonyl-Directed Reaction Systems

2021 ◽  
Author(s):  
Roman Kleinmans ◽  
Omar Apolinar ◽  
Joseph Derosa ◽  
Malkanthi Karunananda ◽  
Zi-Qi Li ◽  
...  
Keyword(s):  
Functional Group ◽  
Coupling Reaction ◽  
Building Blocks ◽  
Binding Mode ◽  
Nickel Catalysis ◽  
Mechanistic Studies ◽  
Reaction Systems ◽  
Cross Coupling Reaction ◽  
Wide Range ◽  
Shed Light

<div><p>A conjunctive cross-coupling reaction of alkenyl ketones, aryl iodides, and arylboronic esters under nickel catalysis is reported. The reaction delivers the desired 1,2-diarylated products with moderate to excellent regiocontrol using a diverse array of ketone starting materials, as illustrated across over 40 examples. To showcase the versatility of this method, a representative product is diversified into a wide range of synthetically useful building blocks, that are not readily accessible via existing 1,2-diarylation reactions. Preliminary mechanistic studies shed light on the binding mode of the substrate, and Hammett analysis shows the effect of electronic factors on initial rates. To our knowledge, this method represents the first example of catalytic 1,2-diarylation of an alkene, directed by a native ketone functional group.</p></div>

scholarly journals Nickel-Catalyzed 1,2-Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3-Trifunctionalized Building Blocks

2019 ◽  
Author(s):  
Joseph Derosa ◽  
Taeho Kang ◽  
Van Tran ◽  
Steven Wisniewski ◽  
Malkanthi Karunananda ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Functional Group ◽  
Cross Coupling ◽  
Building Blocks ◽  
Step Count ◽  
Bioactive Molecules ◽  
Aryl Iodides ◽  
Boronic Esters ◽  
Synthetic Utility

A nickel-catalyzed conjunctive cross-coupling of alkenyl carboxylic acids, aryl iodides, and aryl/alkenyl boronic esters is reported. The reaction delivers the desired 1,2-diarylated and 1,2-arylalkenylated products with excellent regiocontrol. To demonstrate the synthetic utility of the method, a representative product is prepared on gram scale and then diversified to eight 1,2,3-trifunctionalized building blocks using two-electron and one-electron logic. Using this method, three routes toward bioactive molecules are improved in terms of yield and/or step count. This method represents the first example of catalytic 1,2-diarylation of an alkene directed by a native carboxylate functional group.

Directed Nickel-Catalyzed 1,2-Dialkylation of Alkenes

2018 ◽  
Author(s):  
Joseph Derosa ◽  
Vincent A. van der Puyl ◽  
Van T. Tran ◽  
Mingyu Liu ◽  
Keary Engle
Keyword(s):  
Cross Coupling ◽  
Alkyl Halides ◽  
Wide Range ◽  
Directing Group ◽  
Optimized Conditions

A nickel-catalyzed conjunctive cross-coupling of non-conjugated alkenes, alkyl halides, and alkylzinc reagents is reported. Regioselectivity is controlled by chelation of a removable bidentate 8-aminoquinoline directing group. Under optimized conditions, a wide range of 1,2-dialkylated products can be accessed in moderate to excellent yields. To the best of our knowledge, this report represents the first example of three-component 1,2-dialkylation of non-conjugated alkenes to introduce differentiated alkyl fragments.

scholarly journals Nickel-Catalyzed 1,2-Diarylation of Alkenyl Ketones: A Comparative Study of Carbonyl-Directed Reaction Systems

2021 ◽  
Author(s):  
Roman Kleinmans ◽  
Omar Apolinar ◽  
Joseph Derosa ◽  
Malkanthi Karunananda ◽  
Zi-Qi Li ◽  
...  
Keyword(s):  
Functional Group ◽  
Coupling Reaction ◽  
Building Blocks ◽  
Binding Mode ◽  
Nickel Catalysis ◽  
Mechanistic Studies ◽  
Reaction Systems ◽  
Cross Coupling Reaction ◽  
Wide Range ◽  
Shed Light

<div><p>A conjunctive cross-coupling reaction of alkenyl ketones, aryl iodides, and arylboronic esters under nickel catalysis is reported. The reaction delivers the desired 1,2-diarylated products with moderate to excellent regiocontrol using a diverse array of ketone starting materials, as illustrated across over 40 examples. To showcase the versatility of this method, a representative product is diversified into a wide range of synthetically useful building blocks, that are not readily accessible via existing 1,2-diarylation reactions. Preliminary mechanistic studies shed light on the binding mode of the substrate, and Hammett analysis shows the effect of electronic factors on initial rates. To our knowledge, this method represents the first example of catalytic 1,2-diarylation of an alkene, directed by a native ketone functional group.</p></div>

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