DBU-Catalyzed Rearrangement of Secondary Propargylic Alcohols: An Efficient and Cost-Effective Route to Chalcone Derivatives

Rimpa De; Antony Savarimuthu; Tamal Ballav; Pijush Singh; Jayanta Nanda; Avantika Hasija; Deepak Chopra; Mrinal K. Bera

doi:10.1055/s-0040-1707909

Synlett, Table of Contents

Synlett 2020; 31(16): 1587-1592
DOI: 10.1055/s-0040-1707909

letter

DBU-Catalyzed Rearrangement of Secondary Propargylic Alcohols: An Efficient and Cost-Effective Route to Chalcone Derivatives

Rimpa De

^aDepartment of Chemistry, Indian Institute of Engineering Science and Technology (IIEST), Shibpur P.O.-Botanic Garden, Howrah-711 103 (WB), India

,

Antony Savarimuthu

^bDepartment of Chemistry, St. Xavier’s College (Autonomous), Palayamkottai, Tamil Nadu-627 002, India

,

Tamal Ballav

^aDepartment of Chemistry, Indian Institute of Engineering Science and Technology (IIEST), Shibpur P.O.-Botanic Garden, Howrah-711 103 (WB), India

,

Pijush Singh

^aDepartment of Chemistry, Indian Institute of Engineering Science and Technology (IIEST), Shibpur P.O.-Botanic Garden, Howrah-711 103 (WB), India

,

Jayanta Nanda

^aDepartment of Chemistry, Indian Institute of Engineering Science and Technology (IIEST), Shibpur P.O.-Botanic Garden, Howrah-711 103 (WB), India

,

Avantika Hasija

^cDepartment of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhauri, Bhopal-462066, India Email: mrinalkbera26@gmail.com

,

Deepak Chopra

^cDepartment of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhauri, Bhopal-462066, India Email: mrinalkbera26@gmail.com

,

Mrinal K. Bera ∗

^aDepartment of Chemistry, Indian Institute of Engineering Science and Technology (IIEST), Shibpur P.O.-Botanic Garden, Howrah-711 103 (WB), India

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Abstract

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Abstract

A 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-catalyzed rearrangement of diarylated secondary propargylic alcohols to give α,β-unsaturated carbonyl compounds has been developed. The typical 1,3-transposition of oxy functionality, characteristic of Mayer–Schuster rearrangements, is not observed in this case. A broad substrate scope, functional-group tolerance, operational simplicity, complete atom economy, and excellent yields are among the prominent features of the reaction. Additionally, the photophysical properties and crystal-structure-packing behavior of selected compounds were investigated and found to be of interest.

Key words

rearrangement - propargylic alcohols - DBU - chalcones - allenols - organocatalysis

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References

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27 Chalcones 2a–u; General Procedure DBU (10 mol%) was added to a solution of the appropriate propargylic alcohol 1 (1.0 equiv) in dry MeCN (0.2 M) in a sealed tube, and the solution was mixed well by manual shaking. N₂ gas was flashed into the tube, and the cap was quickly closed. The sealed tube was placed in an oil bath at 80 °C, and the mixture was stirred for 18 h until the substrate was completely consumed (TLC). The mixture was then allowed to cool to r.t. and the reaction was quenched with H₂O (10 mL). The product was extracted with Et₂O (3 × 20 mL), and the combined organic layers were washed with brine (10 mL), dried (Na₂SO₄), and concentrated under reduced pressure. The crude product was purified by column chromatography [silica gel (100–200 mesh), PE–EtOAc (10:1)]. (2E)-1,3-Diphenylprop-2-en-1-one (2a) White solid; yield: 43.2 mg (86%); mp 54–56 °C. IR (ATR): 3059 (=CH), 1658 (C=O), 1598 (C=C) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ =8.02 (d, J = 8.0 Hz, 2 H), 7.81 (d, J = 16.0 Hz, 1 H), 7.63 (dd, J = 8.0, 4.0 Hz, 2 H), 7.59–7.48 (m, 4 H), 7.42–7.40 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 190.6, 144.9, 138.2, 134.9, 132.9, 130.6, 129.0, 128.7, 128.6, 128.5, 122.2.

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