Synlett 2023; 34(11): 1275-1279
DOI: 10.1055/a-2024-4675
letter

Synthesis of γ-Aryl Medium-Sized Cyclic Enones by a Domino 4π-Electrocyclic Reaction/Heck–Matsuda Arylation Sequence at Ambient Temperature

Tomohiro Ito
,
Nao Takeuchi
,
,
,
Kiyosei Takasu
This work was funded by JSPS KAKENHI (Grant Number 19H03350), MEXT KAKNHI (Grant Number JP21H05211) in Digi-TOS and BINDS from AMED (Grants Numbers 22ama121042j0001 and 22ama121034j0001).


Abstract

Bicyclo[n.2.0]cyclobutenes were transformed into medium-sized cyclic γ-aryl enones by using a cationic aryl palladium(II) species generated from a diazonium salt. The reaction proceeded at ambient temperature by capturing the cis,trans-cycloalkadiene intermediate generated through a conrotatory 4π-electrocyclic ring-opening reaction, followed by a Heck–Matsuda arylation sequence. Optically pure γ-aryl enones were also synthesized by using a point-to-planar-to-point chirality-transfer process.

Supporting Information



Publication History

Received: 09 January 2023

Accepted after revision: 01 February 2023

Accepted Manuscript online:
01 February 2023

Article published online:
02 March 2023

© 2023. Thieme. All rights reserved

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  • References and Notes

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  • 17 γ-Arylcyclooctenones 5; General Procedure (Conditions A) A test tube was charged with Pd(OAc)2 (0.014 mmol) together with the appropriate diazonium tetrafluoroborate 6 (0.41 mmol) and cyclobutene 1 (0.27 mmol). Ag2CO3 (0.54 mmol) and MeCN (0.20 M) were added to the mixture under argon, and the resulting slurry was vigorously stirred for 38 h. Et2O was added to the mixture, which was then stirred for a further 15 min. The resulting slurry was filtered through Celite, and the filter cake was washed with Et2O. The filtrate was concentrated under reduced pressure to remove the solvent and the residue was dissolved in Et2O. Silica gel was added to the solution and the mixture was stirred for 30 min. The slurry was then filtered and the filter cake was washed with Et2O. Concentration of the filtrate gave a crude product that was dissolved in CHCl3 and purified by column chromatography (silica gel, hexane–EtOAc or hexane–EtOAc). Methyl 3-(4-Methylphenyl)-8-oxocyclooct-1-ene-1-carboxylate (5aa) Colorless oil; yield: 67 mg (90%). Rf = 0.38 (hexane–Et2O, 4:1). IR (ATR): 2928, 2855, 1724, 1697, 1636, 1512, 1454, 1435, 1254, 1223, 1107, 1065 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.19 (d, J = 5.2 Hz, 1 H), 7.11 (d, J = 7.9 Hz, 2 H), 7.02 (d, J = 11.0 Hz, 2 H), 3.74 (s, 3 H), 3.49 (ddd, J = 10.7, 2.4, 2.4 Hz, 1 H), 2.67 (ddd, J = 16.0, 3.3, 3.3 Hz, 1 H), 2.58 (ddd, J = 14.0, 11.0, 3.0 Hz, 1 H), 2.31 (s, 3 H), 2.10–1.97 (m, 1 H), 1.97–1.86 (m, 2 H), 1.86–1.77 (m, 1 H), 1.77–1.62 (m, 2 H). 13C NMR (126 MHz, CDCl3): δ = 209.2, 164.4, 147.9, 139.4, 136.5, 130.5, 129.4, 127.5, 52.3, 46.9, 44.0, 30.7, 27.9, 22.1, 20.9. HRMS (ESI): m/z [M + H]+ calcd for C17H21O3: 273.1485; found: 273.1484.