Green and rapid acid-catalyzed ynamide skeletal rearrangement and stereospecific functionalization with anisole derivatives

Mutra, Mohana Reddy; Chandana, T. L.; Wang, Yun-Jou; Wang, Jeh-Jeng

doi:10.1039/d3gc02460a

Green Chem.

2023

DOI: 10.1039/d3gc02460a

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Green and rapid acid-catalyzed ynamide skeletal rearrangement and stereospecific functionalization with anisole derivatives

Mohana Reddy Mutra,

T. L. Chandana,

Yun-Jou Wang

et al.

Abstract: Environmentally-friendly acid-catalyzed ynamide N-Csp bond clevage and skeletal rearrangement and chemo-regio- and stereospecific functionalization with nucleophiles is of great interest in synthetic chemistry. But, it has remarkable regio- and stereospecific...

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2024

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Cited by 7 publications

References 48 publications

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Base‐Promoted Structural Rearrangement of Ynamide and Simultaneous N‐Desulfonylation

Reddy Mutra,

Chandana,

Chang

et al. 2024

Adv Synth Catal

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The strategy of ynamide structural rearrangement is crucial in modern organic synthesis. The distinct carbon atoms in ynamides have different selectivity under various reaction conditions. Herein, we developed a base‐promoted regioselective and chemoselective cascade cyclization, ynamide N–Csp bond cleavage, selective intramolecular 1,3‐migration, and simultaneous N‐desulfonylation strategy for the synthesis of 2‐phenyl‐3‐(phenylethynyl)‐1H‐indole derivatives within a time of 15 min. We observed multiple bond breaking (‐N–Ts, and Csp2–Ts, Csp2–I/Csp2–SePh) from (E)‐3‐(1‐iodo‐2‐phenyl‐2‐tosylvinyl)‐2‐phenyl‐1‐tosyl‐indole/(E)‐2‐phenyl‐3‐(2‐phenyl‐1‐(phenylselanyl)‐2‐tosylvinyl)‐1‐tosyl‐indole derivatives to achieve 2‐phenyl‐3‐(phenylethynyl)‐1H‐indole in 15–60 min using our standard reaction conditions. A gram‐scale experiment and the postsynthetic transformation of the synthesized 2‐phenyl‐3‐(phenylethynyl)‐1H‐indole were conducted to exhibit the advantages of our synthetic methodology. The developed methodology has multiple advantages: a rapid reaction rate, regioselectivity and chemoselectivity, transition metal and acid oxidant free, preventing resource waste and a time‐consuming process in deprotecting steps, broad substrate scope, mild reaction condition, simple setup, ease of handle, gram‐scale experiment, and synthetic product transformations.

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Base‐Promoted Structural Rearrangement of Ynamide and Simultaneous N‐Desulfonylation

Reddy Mutra,

Chandana,

Chang

et al. 2024

Adv Synth Catal

Self Cite

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Metal Additive–Free Iodine–Promoted Reorganization of Ynamide‐Ynes and Stereoselective 1,2‐Diiodination

Reddy Mutra,

Chandana,

Wang

et al. 2024

Chemistry An Asian Journal

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We report a metal additive–free iodine‐promoted one‐step structural reorganization of ynamide‐ynes and simultaneous stereoselective 1,2‐diiodination of the migrated alkyne to form stereospecific tetrasubstituted alkenyl diiodo‐tethered indoles (E‐isomer). Molecular iodine is cost effective, user friendly, less toxic, commercially available, and easy to handle. The key features of the reaction include metal– and additive–free environment, selectivity, structural reorganization, mild reaction conditions, simple workup, and gram‐scale synthesis. This transformation generates multiple bonds [nitrogen (N)–carbon (C)sp2, Csp2–Csp2, 2 Csp2–iodine (I)] via N–Csp bond cleavage in ynamide‐ynes.

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4‐Methyltetrahydropyran: A Versatile Alternative Solvent for the Preparation of Chiral BINOL Catalysts and the Asymmetric Alkylation of Aldehydes

Marra,

De Nardi,

Rossi

et al. 2024

Eur J Org Chem

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We herein report that the highly hydrophobic ether 4‐MeTHP constitutes a promising resource for the development of sustainable synthetic methodologies grounded on the use of organometallic reagents. The beneficial effects of 4‐MeTHP as reaction media are illustrated in the organolithium‐promoted anionic ortho‐Fries rearrangement of 1,1’‐bi‐2‐naphthol (BINOL)‐based carbamates under bench‐type conditions. The use of 4‐MeTHP induces a remarkable and unexpected stability of the organolithiums species, enabling the efficient preparation of chiral (bis)carboxamide catalysts. Furthermore, superior performances of 4‐MeTHP than other environmentally responsible solvents are observed using the synthesized BINOL catalysts in the asymmetric addition of organozinc reagents to aldehydes. Spectroscopic studies in solution suggest that 4‐MeTHP plays a key role in these reactions by inducing the preferential formation of a reactive monomeric dinuclear complex. This methodology allows for the asymmetric assembly of enantioenriched secondary alcohols in good yields and high stereoselectivity, working at 0 °C and under air.

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Green and rapid acid-catalyzed ynamide skeletal rearrangement and stereospecific functionalization with anisole derivatives

Abstract: Environmentally-friendly acid-catalyzed ynamide N-Csp bond clevage and skeletal rearrangement and chemo-regio- and stereospecific functionalization with nucleophiles is of great interest in synthetic chemistry. But, it has remarkable regio- and stereospecific...

Cited by 7 publications

References 48 publications

Base‐Promoted Structural Rearrangement of Ynamide and Simultaneous N‐Desulfonylation

Base‐Promoted Structural Rearrangement of Ynamide and Simultaneous N‐Desulfonylation

Metal Additive–Free Iodine–Promoted Reorganization of Ynamide‐Ynes and Stereoselective 1,2‐Diiodination

4‐Methyltetrahydropyran: A Versatile Alternative Solvent for the Preparation of Chiral BINOL Catalysts and the Asymmetric Alkylation of Aldehydes

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