Langlois Reagent Mediated Tandem Cyclization of o-Hydroxyaryl Enaminones for the Synthesis of 3-(Trifluoromethyl)chromones

Pradeepkumar Thota; Kalidasu Sheelam; Shrinivas Kottawar; K. Shivakumar; Muralidharan Kaliyaperumal; Satyanarayana Yennam; Manoranjan Behera

doi:10.1055/a-1906-3382

Synlett, Table of Contents

Synlett 2022; 33(16): 1660-1664
DOI: 10.1055/a-1906-3382

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Langlois Reagent Mediated Tandem Cyclization of o-Hydroxyaryl Enaminones for the Synthesis of 3-(Trifluoromethyl)chromones

Pradeepkumar Thota

^aChemistry Services, Aragen Life Sciences, Survey Nos: 125 (part) and 126, IDA Mallapur, Hyderabad-500076, Telangana, India

^bDepartment of Chemistry, School of Science, Gandhi Institute of Technology and Management (GITAM; Deemed to be a university), Hyderabad Campus, Telangana-502329, India, India

,

Kalidasu Sheelam

^aChemistry Services, Aragen Life Sciences, Survey Nos: 125 (part) and 126, IDA Mallapur, Hyderabad-500076, Telangana, India

,

Shrinivas Kottawar

^aChemistry Services, Aragen Life Sciences, Survey Nos: 125 (part) and 126, IDA Mallapur, Hyderabad-500076, Telangana, India

,

K. Shivakumar

^bDepartment of Chemistry, School of Science, Gandhi Institute of Technology and Management (GITAM; Deemed to be a university), Hyderabad Campus, Telangana-502329, India, India

,

Muralidharan Kaliyaperumal

^aChemistry Services, Aragen Life Sciences, Survey Nos: 125 (part) and 126, IDA Mallapur, Hyderabad-500076, Telangana, India

,

Satyanarayana Yennam

^aChemistry Services, Aragen Life Sciences, Survey Nos: 125 (part) and 126, IDA Mallapur, Hyderabad-500076, Telangana, India

,

Manoranjan Behera∗

^aChemistry Services, Aragen Life Sciences, Survey Nos: 125 (part) and 126, IDA Mallapur, Hyderabad-500076, Telangana, India

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Abstract

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Abstract

An efficient and simple synthesis of various 3-(trifluoromethyl)chromones from enamino ketones is described. The key step in the synthesis involves the introduction of a trifluoromethyl (CF₃) moiety onto a chromone structure. The significant features of this method include simple operational procedures, the high purity and yield of the product, and excellent regioselectivity.

Key words

trifluoromethylation - Langlois reagent - enamino ketones - trifluoromethylchromones - copper acetate

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References

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27 3-(Trifluoromethyl)chromone (5a): Typical Procedure CF₃SO₂Na (326 mg, 2.094 mmol), TBHP (283 mg, 3.14 mmol), and Cu(OAc)₂ (9 mg, 0.052 mmol) were added sequentially to a stirred solution of enaminone 4a (200 mg, 1.047 mmol) in DMSO (5 mL), and the mixture was stirred at RT for 16 h. When the reaction was complete (TLC), the mixture was diluted with EtOAc and washed with H₂O. The organic layer was separated and concentrated, and the crude product was purified by column chromatography (silica gel, EtOAc–hexane) to give an off-white solid; yield: 174 mg (77%); mp 99–102 °C. FTIR (KBr): 3084, 1658, 1465, 1398, 1350, 1267, 1122, 848, 756 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 9.01 (d, J = 0.8 Hz, 1 H), 8.13 (dd, J = 1.6, 8 Hz, 1 H), 7.39–7.896 (m, 1 H), 7.78 (d, J = 8.4 Hz, 1 H), 7.62–7.58 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 172.79, 155.99, 155.78, 155.71, 134.81, 126.45, 126.18, 123.505, 120.800 (q, J = 270.2 Hz, CF₃), 118.29. ¹⁹F NMR (CDCl₃): δ = –62.76 (s, CF₃). MS (EI): m/z (%) = 214 (100) [M + H]⁺. HRMS: (ESI): m/z [M + H]⁺calcd for C₁₀H₆F₃O₂: 215.0320; found: 215.2598.

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