A Precise Route to Tetrasubstituted Allyl Amines via Regioselective Dicarbofunctionalization of Masked Propargyl Amines DOI
Aradhana Sahoo, Shubham Dutta, Akhila K. Sahoo

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(45), P. 9746 - 9751

Published: Nov. 7, 2024

Allyl amines are vital components in various biologically important molecules and play a significant role their function. Presently, most methods geared toward the preparation of di- trisubstituted allyl amines, leaving gap for development more versatile approaches. We herein describe an approach to yield tetrasubstituted through palladium (Pd)-catalyzed regioselective dicarbofunctionalization masked N-phthalimide-protected propargyl amines. The cationic Pd-intermediate conjunction with amine exerts collective control reaction regioselectivity. This method accommodates wide range alkynes, aryl boronic acids, diazonium salts offering direct access unusual

Language: Английский

Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes DOI Creative Commons
Tianyu Long, Chen Zhu, Ling Li

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Language: Английский

Citations

51
Regioselective Difunctionalization and Annulation of Ynamide DOI
Shubham Dutta, Rajendra K. Mallick, Akhila K. Sahoo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 8, 2023

Abstract The use of ynamides in organic synthesis has gained significant attention due to their ability provide access complex molecular structures through transformations such as 1,2‐difunctionalization and annulation reactions. These reactions enable the formation highly functionalized N‐bearing olefins unusual heterocycles. In this minireview, we present a systematic overview regioselective difunctionalization ynamides. We discuss multi‐component reactions, radical‐triggered functionalizations across carbon–carbon multiple bonds bifunctional reagents ynamides, highlighting potential expanding substrate scope. Furthermore, insights into mechanistic breakthroughs that have been achieved recent years development these Finally, emphasize promising future prospects versatile building blocks for architectures.

Language: Английский

Citations

28
Stereoselective synthesis of substituted 1,3-dienes from propargylic esters: electrophilic-metal or redox catalysis? DOI

Mengfu Dai,

Liangliang Song, Liang‐An Chen

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(5), P. 1384 - 1396

Published: March 22, 2024

Language: Английский

Citations

10
Nickel-Catalyzed Asymmetric Cross-Electrophile trans-Aryl-Benzylation of α-Naphthyl Propargylic Alcohols DOI
Zhiyang Lin,

Weitao Hu,

Linchuan Zhang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6795 - 6803

Published: May 3, 2023

Herein, we report a nickel-catalyzed asymmetric three-component trans-dicarbofunctionalization of β-substituted α-naphthyl propargylic alcohols using readily available aryl and benzyl halides as the coupling partners under reductive conditions. This cross-electrophile strategy enables synthesis various axially chiral allylic bearing tetrasubstituted olefinic unit in complete regio- E selectivity, well high enantiocontrol. Relying on hydroxyl group functional handle, such structural motifs are successfully derivatized into diverse functional-group-rich alkenes.

Language: Английский

Citations

18
Regiodivergent and Stereoselective Synthesis of Highly Substituted 1,3-Dienes via Arylative Acyloxy Migration of Propargyl Esters DOI

Zhimin Sun,

Mengfu Dai,

Chencheng Ding

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(32), P. 18115 - 18125

Published: Aug. 1, 2023

We report the first catalyst-controlled regiodivergent method that enables synthesis of structurally diverse 1,2,3,4-tetrasubstituted conjugated dienes with excellent regio- and stereochemical outcomes from same set readily available propargyl esters diaryliodonium salts. In this diene chemistry, in situ generated, highly electrophilic aryl-CuIII complex serves not only as a π-Lewis acid catalyst for alkyne activation/acyloxy migration but also an aryl electrophile equivalent. The competitive arylative 1,2- 1,3-acyloxy patterns are exquisitely dictated by Cu Au/Cu relay catalyses, respectively, providing modular attractive approach to traditionally inaccessible tetrasubstituted 1,3-dienes manner. Finally, synthetic utility is demonstrated further derivatization into array useful compounds.

Language: Английский

Citations

16
Copper-Catalyzed Regio- and Stereoselective Hydroarylation of Ynamide DOI
Avijit Maity, Akhila K. Sahoo

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(2), P. 852 - 863

Published: Jan. 3, 2024

Presented herein is a copper-catalyzed

Language: Английский

Citations

5
Remote-carbonyl-directed sequential Heck/isomerization/C(sp2)–H arylation of alkenes for modular synthesis of stereodefined tetrasubstituted olefins DOI Creative Commons

Runze Luan,

Ping Lin, Kun Li

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 26, 2024

Abstract Modular and regio-/stereoselective syntheses of all-carbon tetrasubstituted olefins from simple alkene materials remain a challenging project. Here, we demonstrate that remote-carbonyl-directed palladium-catalyzed Heck/isomerization/C(sp 2 )–H arylation sequence enables unactivated 1,1-disubstituted alkenes to undergo stereoselective terminal diarylation with aryl iodides, thus offering concise approach construct stereodefined in generally good yields under mild conditions; diverse carbonyl groups are allowed act as directing groups, various can be introduced at the desired position simply by changing iodides. The stereocontrol protocol stems compatibility between E / Z isomerization alkenyl C(sp arylation, where vicinal group-directed -type intermediate product thermodynamically drives reversible isomerization. Besides, group not only promotes Pd-catalyzed sequential transformations weak coordination, but also avoids byproducts caused other possible β -H elimination.

Language: Английский

Citations

5
Three Component syn‐1,2‐Arylmethylation of Internal Alkynes** DOI
Shubham Dutta, Akhila K. Sahoo

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 26, 2023

A Pd-catalyzed three-component syn-1,2-arylmethylation of internal alkynes (ynamides/yne-acetates/alkynes) is described. The readily available and bench stable coupling partners iodo-arenes, methyl boronic acid are successfully used in this strategy to access the methyl-containing tetra-substituted olefins; scope broad showing excellent functional-group tolerance. Notably, transformation regio- as well stereoselective. biologically relevant motifs (BRM) bearing iodo-arenes ynamides also for late-stage alkynes. Aryl-alkylation, aryl-trideuteriomethylation, alkynyl-methylation, alkenyl-methylation presented. Me-substituted alkenes further transformed into synthetically important β-amino-indenones α-fluoro-α'-methyl ketones.

Language: Английский

Citations

13
Palladium-Catalyzed Cross-Electrophile Coupling between Aryl Diazonium Salt and Aryl Iodide/Diaryliodonium Salt in H2O–EtOH DOI

Kartic Manna,

Ranjan Jana

Organic Letters, Journal Year: 2023, Volume and Issue: 25(2), P. 341 - 346

Published: Jan. 6, 2023

We report herein a mild highly chemoselective palladium-catalyzed cross-electrophile coupling between readily accessible aromatic diazonium salt and aryl iodide or diaryliodonium in water-ethanol (2:1) medium. Mechanistic studies revealed that ethanol is crucial to generate an active Pd(0) catalyst, the counterion of renders cationic Pd(II) species facilitates subsequent oxidative addition iodide/diaryliodonium salt. Silver(I) was retain catalytic activity palladium, removing ion as precipitate.

Language: Английский

Citations

9
Trifluoromethyl Group (CF3) Induced Regioselective Larock Indole Synthesis from Unsymmetric β-CF3-1,3-enynes DOI

Yan‐Hua Qiu,

Peng-Xiang Ma,

Wen‐Hao Shao

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

The indole skeleton exists widely in natural products, pharmaceuticals, and materials. We disclose here a trifluoromethyl group induced regioselective Larock synthetic method from unsymmetric 2-CF3-1,3-enynes. presence of is determinable for the regioselectivity. Once CF3 was replaced with methyl or phenyl group, ratio 1:1 to 1:1.4 isomers were obtained. This strategy features good regioselectivity, broad substrate scope, high functional tolerance. protocol reported offers an alternative solution rare 3,4-functionalization products further transformed show distinctive reactivity hydroboration–oxidation hydro-bromination.

Language: Английский

Citations

0