Highly Selective TEMPO-catalyzed Hydroxyl Oxidation

doi:10.7503/cjcu20200521

Abstract

Abstract:

Sodium hypochlorite highly selectively oxidizes 3，7-dihydroxyl groups in the cholic acids in the presence of （2，2，6，6-tetramethylpiperidin-1-yl）oxyl（TEMPO） under mild conditions to offer 3-hydroxyl products with high yields. Contrary to the conventional oxidants， the high selectivity of the oxidant provides a more concise route for the conversion of cholic acid compounds.

Key words: （2, 2, 6, 6-Tetramethylpiperidin-1-yl）oxyl（TEMPO）, NaClO, Cholic acid, Regioselectivity, Hydroxyl oxidation

CLC Number:

O621

TrendMD:

WANG Yibo, HUANG Dafu, LIANG Zihao, DING Kai. Highly Selective TEMPO-catalyzed Hydroxyl Oxidation[J]. Chem. J. Chinese Universities, 2020, 41(10): 2211.

Figures/Tables 4

References 19

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Compd.	m. p.(ref.)/℃	¹H NMR(400 MHz, CDCl₃), δ
1b	142—143(137—139^[14])	3.87(d, J=3.8 Hz, 1H, 7β-H), 3.66(s, 3H), 1.00(s, 3H), 0.92(d, J=6.5 Hz, 3H), 0.68(s, 3H)^[14]
2b	118—122(128—129^[13])	3.92(s, 1H, 7β-H), 3.67(s, 3H), 3.39(dd, J=15.1, 13.6 Hz, 1H, 4α-H), 1.00(s, 3H), 0.94 (d, J=6.5 Hz, 3H), 0.70(s, 3H)^[13]
3b	102—104(103—104^[15])	3.66(s, 3H), 3.64—3.57(m, 1H, 7α-H), 1.05(s, 3H), 0.94(d, J=6.4 Hz, 3H), 0.72(s, 3H)^[16]
4b	162—164(174^[11])	4.04(s, 1H), 3.93(s, 1H), 3.67(s, 3H), 3.51—3.32(m, 1H), 1.00(s, 3H), 0.99(d, J=6.4 Hz, 3H), 0.74(s, 3H)^[11]

Compd.	m. p.(ref.)/℃	¹H NMR(400 MHz, CDCl₃), δ
1b	142—143(137—139^[14])	3.87(d, J=3.8 Hz, 1H, 7β-H), 3.66(s, 3H), 1.00(s, 3H), 0.92(d, J=6.5 Hz, 3H), 0.68(s, 3H)^[14]
2b	118—122(128—129^[13])	3.92(s, 1H, 7β-H), 3.67(s, 3H), 3.39(dd, J=15.1, 13.6 Hz, 1H, 4α-H), 1.00(s, 3H), 0.94 (d, J=6.5 Hz, 3H), 0.70(s, 3H)^[13]
3b	102—104(103—104^[15])	3.66(s, 3H), 3.64—3.57(m, 1H, 7α-H), 1.05(s, 3H), 0.94(d, J=6.4 Hz, 3H), 0.72(s, 3H)^[16]
4b	162—164(174^[11])	4.04(s, 1H), 3.93(s, 1H), 3.67(s, 3H), 3.51—3.32(m, 1H), 1.00(s, 3H), 0.99(d, J=6.4 Hz, 3H), 0.74(s, 3H)^[11]

Product	Yield^b(%)	Product	Yield^b(%)
1b	95.1	1b	80.2
2b	64.9	3b	88.1
3b	97.5	4b	78.0

Product	Yield^b(%)	Product	Yield^b(%)
1b	95.1	1b	80.2
2b	64.9	3b	88.1
3b	97.5	4b	78.0

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