2012
DOI: 10.1021/jo301185h
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Aromatic Cations from Oxidative Carbon–Hydrogen Bond Cleavage in Bimolecular Carbon–Carbon Bond Forming Reactions

Abstract: Chromenes and isochromenes react quickly with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form persistent aromatic oxocarbenium ions through oxidative carbon–hydrogen cleavage. This process is tolerant of electron-donating and electron-withdrawing groups on the benzene ring and additional substitution on the pyran ring. A variety of nucleophiles can be added to these cations to generate a diverse set of structures.

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Cited by 66 publications
(29 citation statements)
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“…Laurent has reported (Part‐a, Figure ) the synthesis of substituted 2‐ perfluoroalkyl‐4 H ‐chromenes in the presence of SnCl 4 . Many substituted 2 H ‐chromenes and iso‐chromenes have been synthesized through oxidative carbon‐hydrogen cleavage by Floreancig group . More recently, Shizheng Zhu group reported nucleophilic substitution reaction between 2‐(trifluoromethyl)‐2‐hydroxy‐2 H ‐chromenes and various silyl enol ethers promoted by Lewis acid under stringent reaction conditions and stoichiometric ratio of Lewis acid (Part‐b, Figure ).…”
Section: Figurementioning
confidence: 99%
“…Laurent has reported (Part‐a, Figure ) the synthesis of substituted 2‐ perfluoroalkyl‐4 H ‐chromenes in the presence of SnCl 4 . Many substituted 2 H ‐chromenes and iso‐chromenes have been synthesized through oxidative carbon‐hydrogen cleavage by Floreancig group . More recently, Shizheng Zhu group reported nucleophilic substitution reaction between 2‐(trifluoromethyl)‐2‐hydroxy‐2 H ‐chromenes and various silyl enol ethers promoted by Lewis acid under stringent reaction conditions and stoichiometric ratio of Lewis acid (Part‐b, Figure ).…”
Section: Figurementioning
confidence: 99%
“…The widespread availability and unique nucleophilicity of organoboranes have attracted growing interest in exploring new chemistry beyond the Suzuki–Miyaura coupling, including α‐vinylation of aldehydes,9a transition metal catalyzed additions of boronic acids or boroxines to epoxides,9b oxocarbenium and N ‐acyliminium ions,9cd Lewis acid mediated dialkyl ether synthesis from organotrifluoroborates and acetals,9ef and CH arylation of quinones and electron‐deficient hererocycles such as pyridine and pyrimidine 9hj. Therefore, initially we examined the benzylation of the N ‐acyl THIQ 1 with potassium benzyltrifluoroborate ( 2 a ) at room temperature for reaction optimization (Table 1).…”
Section: Model Reaction Optimization[a]mentioning
confidence: 99%
“…Spectroscopic data are identical to those in the literature. 16 Compound 5h: brown viscous oil; R f = 0.27 (50% EtOAc/petrol); IR (neat) ν max 3336,2934,2853,1699,1612,1595,1462,1323,1227,1086,750, and 729 cm −1 ; 1 H NMR (500 MHz) δ 7.36 (1H, d, J = 7.5 Hz, ArH), 7.20 (1H, t, J = 8.0 Hz, ArH), 6.95 (1H, t, J = 7.5 Hz, ArH), 6.87 (1H, d, J = 8.0 Hz, ArH), 4.89 (1H, dt, J = 7.5, 1.5 Hz, CCH), 4.75 (1H, s, CHN), 3.69 (2H, t, J = 6.5 Hz, CH 2 OH), 2.75 (1H, brs, OH), 2.54−2.52 (2H, m, CH 2 N), 2.41−2.34 (4H, m, CH 2 N and C CHCH 2 ), 1.73 (2H, quint, J = 7.0 Hz, CH 2 CH 2 CH 2 ), 1.56−1.48 (4H, m, 2 × CH 2 ), 1.40−1.36 (2H, m, CH 2 ); 13 C NMR (125 MHz) δ 158.0 (ArCO), 153.3 (OCCHAr), 129.3 (ArCH), 126.3 (ArCH), 125.9 (ArC), 121.6 (ArCH), 109.5 (ArCH), 105.1 (CCHAr), 66.9 (CHN), 62.1 (CH 2 OH), 49.4 (2 × CH 2 N), 32.5 (CH 2 ), 26.3 (2 × CH 2 ), 24.5 (CH 2 ), 21.5 (CCHCH 2 ); HRESIMS calcd for C 17 H 24 NO 2 (M + H) + 274.1807; found 274.1807.…”
Section: ■ Experimental Sectionmentioning
confidence: 99%