Synthesis of Cytogenin Analogues by C(sp2)–H Functionalization under Ruthenium(II) Catalysis, and DFT Analysis

Ashish Joshi; Lilesh Rambhai Chavada; Mridula Choudhary; Dhruvilkumar Patel; Priyanka Mishra; Sneha Patil; Balasubramanian Sridhar; Saurabh Kumar Singh; Ashok Kumar Pandey

doi:10.1055/a-2564-5919

Synlett, Table of Contents

Synlett
DOI: 10.1055/a-2564-5919

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Emerging Trends in Organic Chemistry: A Focus on India

Synthesis of Cytogenin Analogues by C(sp²)–H Functionalization under Ruthenium(II) Catalysis, and DFT Analysis

Ashish Joshi‡

^aFluoro-Agrochemicals Division, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Tarnaka, Telangana 500007, India URL: https://sites.google.com/view/akplab/home

^bAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India

,

Lilesh Rambhai Chavada‡

^aFluoro-Agrochemicals Division, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Tarnaka, Telangana 500007, India URL: https://sites.google.com/view/akplab/home

^bAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India

,

Mridula Choudhary

^cDepartment of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, Telangana, 502285, India URL: https://sites.google.com/view/skslab/home

,

Dhruvilkumar Patel

^aFluoro-Agrochemicals Division, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Tarnaka, Telangana 500007, India URL: https://sites.google.com/view/akplab/home

,

Priyanka Mishra

^aFluoro-Agrochemicals Division, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Tarnaka, Telangana 500007, India URL: https://sites.google.com/view/akplab/home

,

Sneha Patil

^aFluoro-Agrochemicals Division, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Tarnaka, Telangana 500007, India URL: https://sites.google.com/view/akplab/home

,

Balasubramanian Sridhar

^bAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India

^dDepartment of Analytical and Structural Chemistry, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Tarnaka, Telangana 500007, India

,

Saurabh Kumar Singh∗

^cDepartment of Chemistry, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, Telangana, 502285, India URL: https://sites.google.com/view/skslab/home

,

Ashok Kumar Pandey ∗

^aFluoro-Agrochemicals Division, CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad, Tarnaka, Telangana 500007, India URL: https://sites.google.com/view/akplab/home

^bAcademy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India

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Abstract

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This work is dedicated to Professor Deevi Basavaiah, School of Chemistry, University of Hyderabad for his immense contribution to the Baylis–Hillman reaction.

Abstract

The first concise and convenient synthesis of natural products, antibiotics, and anticancer agents resembling cytogenin and other isocoumarins has been achieved by using three components (an N-aroyl β-amino ester, an MBH acetate, and N-bromosuccinimide) under ruthenium(II) catalysis. This method provides intermediate isochroman-1-imines through C(sp²)–H allylation with halocyclization in a single operation. Substrate scope studies, a scale-up, and density functional theory calculations to establish the mechanism of the C–H allylation were carried out.

Key words

ruthenium catalysis - allylation - isochromanimines - isocoumarins - cytogenin analogues

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References

References and Notes

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27 Isochroman-1-imines 5a–n; General Procedure An oven-dried screwcap tube was charged with the appropriate amino ester 1 (0.2 mmol, 100 mol%), [Ru(p-cymene)Cl₂]₂ (3.05 mg, 0.005 mmol, 2.5 mol%), AgSbF₆ (6.8 mg, 0.02 mmol, 10 mol%), Cu(OAc)₂·H₂O (19.96 mg, 0.10 mmol, 50 mol%), TCE (1 mL, 0.2 M), and methyl 2-(acetoxymethyl)acrylate (2) (0.4 mmol, 200 mol%) under air at r.t. The mixture was stirred at 120 °C for 4 h then cooled to r.t., and filtered through a small pad of Celite with additional TCE (0.5 mL). The filtrate was collected in another screwcap tube and NBS (0.4 mmol, 200 mol%) was added under the open atmosphere at r.t. The mixture was then stirred at r.t. for 4 h. The resulting mixture was diluted with CH₂Cl₂ (2 mL), then concentrated under reduced pressure. The residue was purified by flash column chromatography [silica gel, EtOAc–hexane (1:9)]. Methyl (1Z)-3-(Bromomethyl)-1-[(3-methoxy-3-oxopropyl)imino]-8-methyl-3,4-dihydro-1H-isochromene-3-carboxylate (5a) Sticky liquid; yield: 64 mg, (80%). IR (KBr): 3019, 1736, 1439, 1214, 1056, 742, 667 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.19 (t, J = 7.5 Hz, 1 H), 7.13 (d, J = 7.3 Hz, 1 H), 6.94 (d, J = 7.1 Hz, 1 H), 3.96 (dt, J = 13.8, 6.8 Hz, 1 H), 3.86–3.80 (m, 1 H), 3.78 (d, J = 10.8 Hz, 1 H), 3.69 (s, 4 H), 3.59 (s, 3 H), 3.24 (s, 2 H), 2.71 (t, J = 6.9 Hz, 2 H), 2.58 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 173.6, 169.8, 150.5, 140.0, 133.0, 131.6, 130.0, 126, 125.4, 80.7, 53.1, 51.6, 42.6, 36.5, 35.8, 35.3, 23.1. HRMS (ESI); m/z [M + H]⁺ calcd for C₁₇H₂₁BrNO₅: 398.0603; found: 398.0602.

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