Synlett 2023; 34(03): 263-270
DOI: 10.1055/a-1948-7303
letter

A Novel Method for Preparing Chromones via 1,2-Migration of α-Diazo-Flavanones

Minghao Sun
,
Kejia You
,
Nian Chen
,
Baochun Ma
Financial support from the National Natural Science Foundation of China (grant no 21572084) is much appreciated.


Abstract

A novel method for preparing chromones from α-diazo-flavanones has been developed. Good yields and regioselectivity are obtained through HCl catalysis and Rh2(Oct)4 catalysis. The chromone obtained can undergo a one-pot Diels–Alder reaction to synthesize flavanone propellane in high yield. Mechanisms about 1,2-migration under both catalysts are proposed.

Supporting Information



Publication History

Received: 13 May 2022

Accepted after revision: 21 September 2022

Accepted Manuscript online:
21 September 2022

Article published online:
07 December 2022

© 2022. Thieme. All rights reserved

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  • 10 General Procedure for the Preparation of Chromones 2 CH2Cl2 (2 mL), 1 (0.2 mol, 1 equiv), and HCl (60 μL) (or Rh2(Oct)4, 0.2 mg) were added to a round-bottomed flask with a magnetic stirrer. The reaction was monitored by TLC and quenched by water after its completion. Then solvent was transferred to a dispensing funnel. Saturated brine and EtOAc were added to the funnel to extract the crude product. The organic phase was dried by Na2SO4 for 20 min and concentrated by the rotary evaporator. Further purification was conducted by a silica gel column using petroleum ether/EtOAc (5:1) as the eluent to give the corresponding product 2. 2-Methyl-4H-chromen-4-one (2a1) Pale yellow solid; mp 72–73 ℃. 1H NMR (400 MHz, CDCl3): δ = 8.17 (dd, J = 7.9, 1.7 Hz, 1 H), 7.63 (ddd, J = 8.7, 7.1, 1.7 Hz, 1 H), 7.43–7.34 (m, 2 H), 6.17 (s, 1 H), 2.38 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 176.18, 164.12, 154.43, 131.38, 123.59, 122.86, 121.52, 115.73, 108.53, 18.55. General Procedure for the Preparation of 3 or 4 CH2Cl2 (2 mL), 2 (0.2 mol, 1 equiv), and olefin (1 mmol, 5 equiv) were added to a quartz flask with a magnetic stirrer. Then the flask was irradiated by a lamp with a wavelength of 365 nm. The reaction was monitored by TLC and quenched by water after its completion. Then solvent was transferred to a dispensing funnel. Saturated brine and EtOAc were added to the funnel to extract the crude products. The organic phase was dried by Na2SO4 for 20 min and concentrated by the rotary evaporator. Further purification was conducted by a silica gel column using petroleum ether/EtOAc (30:1) as the eluent to give the corresponding product 3 or 4. (4aR,4bR,10aS,10bS)-1,2,3,4,4a,10b-hexahydro-10H-4b,10a-Butanobenzo[3,4]cyclobuta[1,2-b]chromen-10-one (3s) Pale yellow solid; mp 34–38℃. 1H NMR (400 MHz, CDCl3): δ = 7.89 (dd, J = 7.7, 1.8 Hz, 1 H), 7.44 (ddd, J = 8.0, 7.7, 1.8 Hz, 1 H), 6.99–6.93 (m, 2 H), 2.79–2.71 (m, 1 H), 2.36–2.20 (m, 2 H), 1.97–1.90 (m, 1 H), 1.78–1.55 (m, 8 H), 1.50–1.32 (m, 5 H), 0.99–0.88 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ = 193.70, 160.56, 135.64, 127.60, 120.73, 119.04, 118.69, 88.54, 52.91, 47.09, 46.73, 30.85, 26.60, 26.10, 25.97, 25.13, 24.94, 23.02, 22.45. HRMS (ESI): m/z calcd for C19H22O2 + H [M + H]+: 283.1620; found: 283.1616. Procedure for the One-Pot Preparation of 3s CH2Cl2 (2 mL), 1s (0.2 mol, 1 equiv) and HCl (60 μL) were added to a quartz flask with a magnetic stirrer. After stirring for 30 min, cyclohexene (0.1 mL, 5 equiv) was added. Then the mixture was irradiated by a lamp with a wavelength of 365 nm. After 6 h, the mixture was transferred to a dispensing funnel. Saturated brine and EtOAc were added to the funnel to extract the crude products. The organic phase was dried by Na2SO4 for 20 min and concentrated by the rotary evaporator. Further purification was conducted by a silica gel column using petroleum ether/EtOAc (30:1) as the eluent to give the corresponding product 3s. Analytical data are provided in the Supporting Information.