Metal-Free Remote C–H Bond Amidation of 8-Amidoquinolines on the C5 Position under Mild Conditions

Ji, Dezhong; He, Xin; Xu, Yizhu; Xu, Ziyue; Bian, Yuchen; Liu, Weixing; Zhu, Qihua; Xu, Yungen

doi:10.1021/acs.orglett.6b01980

Cited by 66 publications

(18 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…7 In 2016, Xu and co-workers reported a PhI(OAc) 2 -mediated C-H bond amidation of 8-amidoquinolines at the C5 position by using dibenzenesulfonimides under metal-free conditions [Scheme 1(a)]. 8 At about the same time, we developed a PhI(OPiv) 2 -mediated C5-amination of 8-amidoquinolines by using N-fluorobenzenesulfonimide (NFSI) as the nitrogen source. This method can also be applied to the amination of anilides to give the para-amination products with high regioselectivity [Scheme 1 (b)].…”

Section: Letter Syn Lettmentioning

confidence: 99%

Remote Oxidative C–H Amidation of Anilides with Dibenzenesulfonimides under Metal-Free Conditions

Xiang

Lan

Zhang

et al. 2018

Synlett

View full text Add to dashboard Cite

General Information1 H NMR, 13 C NMR spectra were recorded on a Bruker DPX-400 spectrometer with CDCl 3 as the solvent and TMS as an internal standard, operating at 400 MHz for 1 H NMR and 100 MHz for 13 C NMR. Melting points were measured by SGW X-4A microscopic apparatus. HRMS-ESI were measured by Q Exactive LC/HRMS spectrometer. Ethyl acetate and hexane were obtained from commercial sources and used for column chromatography without further purification. Other solvents were purified according to the standard methods. Other chemicals were obtained from commercial sources and used as received unless otherwise noted. All the anilides were synthesized through the coupling between corresponding aryl or alkyl acids and anilines according to previous procedures. 1 White solid, 64.0 mg, 72% yield, °C; 1 H NMR (400 MHz, CDCl 3 ): δ 2.14 (s, 3H), 2.18 (s, 3H), 6.79-6.84 (m, 2H), 7.21 (s, 1H), 7.54 (t, J = 7.54 Hz, 4H), 7.67 (t, J = 7.36 Hz, 2H), 7.92 (d, J = 7.92 Hz, 4H), 7.98 (d, J = 8.48 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 17. 63, 24.57, 122.40, 128.52, 129.06, 129.81, 130.09, 133.23, 133.53, 134.03, 137.86, 139.30, 168.52. HRMS-ESI(m/z): calcd for C 21 H 21 N 2 O 5 S 2 (M+H + ): 445.0886, found 445.0884. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)propionamide (3b)White solid, 65.0 mg, 71% yield, mp 185-186 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 1.22 (t, J = 7.44 Hz, 3H), 2.14 (s, 3H), 2.41 (q, J = 7.39 Hz, 2H), 6.80 (d, J = 8.64 Hz, 1H), 6.84 (s, 1H), 7.22 (s, 1H), 7.54 (t, J = 7.58 Hz, 4H), 7.67 (t, J = 7.28 Hz, 2H), 7.91 (d, J = 8.. HRMS-ESI(m/z): calcd for C 22 H 23 N 2 O 5 S 2 (M+H + ): 459.1043, found 459.1045. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)isobutyramide (3c) White solid, 69.9 mg, 74% yield, mp 166-167 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 1.25 (s, 3H), 1.27 (s, 3H), 2.18 (s, 3H), 2.53-2.61 (m, 1H), 6.81 (d, J = 8.72 Hz, 1H), 6.86 (s, 1H), 7.14 (s, 1H), 7.55 (t, J = 7.56 Hz, 4H), 7.65-7.70 (m, 2H), 7.93 (d, J = 7.96 Hz, 4H), 8.06 (d, J = 8.. HRMS-ESI(m/z): calcd for C 23 H 25 N 2 O 5 S 2 (M+H + ): 473.1199, found, 473.1195. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)cyclopropanecarboxamide(3d)White solid, 59.2 mg, 63% yield, mp 185-187 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 0.86 (d, J = 4.92 Hz, 2H), 1.08 (s, 2H), 1.55-1.59 (m, 1H), 2.19 (s, 3H), 6.78 (d, J = 8.56 Hz, 1H), 6.85 (s, 1H), 7.35 (s, 1H), 7.54 (t, J = 7.54 Hz, 4H), 7.67 (t, J = 7.36 Hz, 2H), 7.97 (d, J = 7.88 Hz, 4H), 8.03 (s, 1H); 13 Light yellow solid, 68.4 mg, 64% yield, mp108-110 °C; 1 H NMR (500 MHz, CDCl 3 ): δ 1.97 (s, 3H), 2.68-2.75 (m, 2H), 3.07 (t, J = 7.35 Hz, 2H), 6.78-6.84 (m, 2H), 7.20-7.34 (m, 6H), 7.50-7.61 (m, 5H), 7.65-7.69 (m, 2H), 7.91-7.94 (m, 3H), 8.00 (d, J = 7.35 Hz, 1H); 13 (m/z): calcd for C 28 H 27 N 2 O 5 S 2 (M+H + ): 535.1356, found 535.1353. N-(2-methyl-4-(N-(phenylsulfonyl)phenylsulfonamido)phenyl)benzamide (3f) White solid, 67.8 mg, 67% yield, mp 167-169 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 2.28 (s, 3H), 6.87 (d, J = 8.64 Hz, 1H), 6.91-6.96 (m, 1H), 7.48-7.51 (m, 2H), 7.5...

show abstract

Section: Letter Syn Lettmentioning

confidence: 99%

Remote Oxidative C–H Amidation of Anilides with Dibenzenesulfonimides under Metal-Free Conditions

Xiang

Lan

Zhang

et al. 2018

Synlett

View full text Add to dashboard Cite

show abstract

“…Subsequently, many groups demonstrated the relevance of this reactivity for several Cu‐catalyzed remote C‐H functionalization reactions such as sulfonation, nitration, chalcogenation, amination, trifluoromethylation, halogenation and other functionalizations on the C5 position of 8‐aminoquinoline amides. More recently, Xu and co‐workers demonstrated C−H amidation of 8‐aminoquinolines proceeding under metal‐free conditions using PIDA as a mediator …”

Section: Figurementioning

confidence: 99%

Metal‐Free Remote C‐H Bond Acetoxylation of 8‐Aminoquinolines on the C5‐Position

et al. 2017

View full text Add to dashboard Cite

Herein, we describe a simple and practical approach for the selective acetoxylation at the C5‐position of 8‐aminoquinoline amides under metal free conditions. Our strategy shows high conversion efficiency, broad substrate scope, and functional group tolerance giving access to various C5‐acetoxylated carboxamides, sulfonamides or phosphinamides in good yields. In addition, the reaction conditions are suitable to scale up and also exhibited high regioselectivity.

show abstract

“…[2h] Recently, the metal‐free hypervalent iodine reagent mediated oxidative para ‐selective C–H amination of 8‐aminoquinolines and anilides with NFSI was reported by Li and co‐workers (Scheme a) . Almost at the same time, Xu and co‐workers developed a method for the C–H bond amidation of 8‐amidoquinolines at the C5 position by using dibenzenesulfonimide as the nitrogen source . Moreover, a similar process was reported with readily available azodicarboxylates (Scheme c) .…”

Section: Introductionmentioning

confidence: 98%

Hexafluoro‐2‐propanol Promotes para‐Selective C–H Amination of Free Anilines with Azodicarboxylates

2017

View full text Add to dashboard Cite

An effective, mild, and clean method for the C–H amination of free anilines with azodicarboxylates in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) without the need for any additional catalysts or reagents was developed. The reaction was found to be highly regioselective and provided a series of p‐aminophenylhydrazine derivatives in excellent yields. Moreover, compatibility with a free amino group makes this protocol an attractive strategy in synthetic chemistry.

show abstract

Metal-Free Remote C–H Bond Amidation of 8-Amidoquinolines on the C5 Position under Mild Conditions

Cited by 66 publications

References 66 publications

Remote Oxidative C–H Amidation of Anilides with Dibenzenesulfonimides under Metal-Free Conditions

Remote Oxidative C–H Amidation of Anilides with Dibenzenesulfonimides under Metal-Free Conditions

Metal‐Free Remote C‐H Bond Acetoxylation of 8‐Aminoquinolines on the C5‐Position

Hexafluoro‐2‐propanol Promotes para‐Selective C–H Amination of Free Anilines with Azodicarboxylates

Contact Info

Product

Resources

About