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 6 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

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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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Optimization of peptide synthesis time and sustainability using novel eco‐friendly binary solvent systems with induction heating on an automated peptide synthesizer

Pacini,

Muthyala,

Aguiar

et al. 2024

Journal of Peptide Science

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On December 12th, 2023, the European Commission took regulatory action to amend Annex XVII of REACH, imposing restrictions on the use of N,N‐dimethylformamide (DMF) within the EU market owing to its high toxicity. Historically, DMF has been widely considered the gold standard for solid‐phase peptide synthesis (SPPS). Being urgent to propose alternative solvents, we tested the suitability of non‐hazardous neat and mixed solvents. Notably, binary solvent mixtures containing dimethyl sulfoxide as one of the solvent partners demonstrated high efficacy in solubilizing reagents while maintaining the desired swelling characteristics of common resins. A series of binary solvent mixtures were tested in automated SPPS, both at room temperature and high temperature, employing the PurePep® Chorus synthesizer, which enabled controlled induction heating between 25 and 90°C with oscillation mixing. The performances were assessed in challenging peptide sequences, i.e., ACP (65–74), and in longer and aggregating sequences like SARS‐CoV‐2 RBM (436–507) and β‐amyloid (1–42). Furthermore, as part of the proposed sustainable approach to minimize the utilization of hazardous solvents, we coupled the novel PurePep EasyClean catch‐and‐release purification technology. This work, addressing regulatory compliance, emphasizes the crucial role of green chemistry in advancing safer and more environmentally friendly practices in SPPS.

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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 6 publications

References 48 publications

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

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

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

Optimization of peptide synthesis time and sustainability using novel eco‐friendly binary solvent systems with induction heating on an automated peptide synthesizer

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