2-Iodoxybenzoic Acid–Dimethyl Sulfoxide (IBX-DMSO)-Promoted Oxidative Aromatization of Spiro[2.5]octa-4,7-dien-6-one

Tong Li; Chaoxing Cui; Yuxia Zhang; Xixi Song; Zechao Wang; Junbiao Chang

doi:10.1055/a-1863-8862

Synlett, Table of Contents

Synlett 2022; 33(15): 1546-1550
DOI: 10.1055/a-1863-8862

letter

2-Iodoxybenzoic Acid–Dimethyl Sulfoxide (IBX-DMSO)-Promoted Oxidative Aromatization of Spiro[2.5]octa-4,7-dien-6-one

Tong Li

^aCollege of Chemistry, Zhengzhou University, No. 100 Science Avenue, Zhengzhou, 450001, P. R. of China

,

Chaoxing Cui

^aCollege of Chemistry, Zhengzhou University, No. 100 Science Avenue, Zhengzhou, 450001, P. R. of China

,

Yuxia Zhang

^bSchool of Mathematics, Zhengzhou University of Aeronautics, No. 15 Wenyuan West Road, Zhengzhou, 450046, P. R. of China

,

Xixi Song∗

^aCollege of Chemistry, Zhengzhou University, No. 100 Science Avenue, Zhengzhou, 450001, P. R. of China

,

Zechao Wang ∗

^cDivision of Molecular Catalysis and Synthesis, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, P. R. of China

,

Junbiao Chang∗

^aCollege of Chemistry, Zhengzhou University, No. 100 Science Avenue, Zhengzhou, 450001, P. R. of China

› Author Affiliations

Abstract

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Abstract

A 2-iodoxybenzoic acid (IBX)–dimethyl sulfoxide (IBX-DMSO)-promoted oxidative aromatization of spiro[2.5]octa-4,7-dien-6-ones has been developed. A series of substrates with various substitutions were transformed into oxidative aromatization products in good to excellent yields. This oxidative aromatization features environmentally friendly reagents, high efficiency, a broad substrate scope, broad functional-group tolerance, and mild reaction conditions.

Key words

metal-free reaction - iodoxybenzoic acid - dimethyl sulfoxide - oxidation - aromatization - spirooctadienones

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References

References and Notes

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12 Dialkyl Aroyl(3,5-dialkyl-4-hydroxyphenyl)malonates 2a–t; General Procedure A 10 mL Schlenk tube equipped with a magnetic stirrer bar was charged with spiro compound 1 (0.1 mmol), IBX (10 mol%), and anhyd DMSO (0.5 mL) under air. The tube was sealed with a plastic screw-cap with a Teflon insert, and the mixture was heated to 100 °C. After 12 h, the mixture was cooled to rt and poured into H₂O (20 mL). The resulting mixture was extracted with EtOAc (3 × 20 mL), and the combined organic layer was washed with brine (3 × 20 mL), dried (MgSO₄), and concentrated. The crude product was then purified by chromatography (silica gel). Diethyl Benzoyl(3,5-di-tert-butyl-4-hydroxyphenyl)malonate (2a) Yellow solid; yield: 45.8 mg (98%); mp 140.1–140.9 °C. IR (neat): 3603, 2961, 1746, 1727, 1679, 1595, 1462, 1435, 1192, 1044, 709 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.65 (t, J = 7.3 Hz, 2 H), 7.42 (t, J = 7.4 Hz, 1 H), 7.28 (d, J = 8.1 Hz, 2 H), 7.26 (s, 1 H), 5.23 (s, 1 H), 4.29–4.23 (m, 4 H), 1.34 (s, 18 H), 1.18 (t, J = 7.1 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 192.1, 167.6, 153.6, 136.0, 135.4, 132.4, 129.5, 128.0, 126.2, 124.3, 74.1, 62.2, 34.4, 30.2, 13.8. HRMS (ESI/Q-TOF): m/z [M + H]⁺ calcd for C₂₈H₃₇O₆: 469.2585; found: 469.2588. Diethyl Benzoyl(4-hydroxy-3,5-dimethylphenyl)malonate (2s) Yellow solid; yield: 36.1 mg (94%); mp 110.0–110.9 °C; IR (neat): 3525, 2939, 1746, 1732, 1669, 1595, 1446, 1185, 1064, 694 cm^–1. ¹H NMR (400 MHz, CDCl₃,): δ = 7.69 (d, J = 7.4 Hz, 2 H), 7.42 (t, J = 7.4 Hz, 1 H), 7.28 (t, J = 7.9 Hz, 2 H), 7.15 (s, 2 H), 4.27–4.22 (m, 4 H), 2.16 (s, 6 H), 1.51 (t, J = 7.1 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 191.8, 167.5, 152.4, 135.7, 132.6, 129.7, 129.1, 128.1, 124.9, 123.2, 73.5, 62.3, 16.2, 13.7. HRMS (ESI/Q-TOF): m/z [M + H]⁺ calcd for C₂₂H₂₅O₆: 385.1646; found: 385.1647.

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