2-Bromo-1,3,2-benzodioxaborole; B-Bromocatecholborane -Drug Synthesis Database

【结构式】

【分子编号】42057

【品名】2-Bromo-1,3,2-benzodioxaborole; B-Bromocatecholborane

【CA登记号】51901-85-0

【分子式】C₆H₄BBrO₂

【分子量】198.81156

【元素组成】C 36.25% H 2.03% B 5.44% Br 40.19% O 16.1%

与该中间体有关的原料药合成路线共 2 条

合成路线1 合成路线2

合成路线1

该中间体在本合成路线中的序号：(XXVIII)

The reaction of the amino group of (XXV) with tBu-ONO, BHF4 and CuCl/CuCl2 gives the expected chloro derivative (XXVI), which is silylated at the OH group with CF3CON(Me)-Tbdms, yielding the silyl ether (XXVII). Elimination of the Mem protecting group of (XXVII) with the bromoboronate (XXVIII) affords the carbinol (XXIX), which is oxidized with DMP and NaClO2 to the corresponding carboxylic acid (XXX).

参考文献中间体

合成目标

【1】 Boger, D.L.; et al.; First and second generation total synthesis of the teicoplanin aglycon. J Am Chem Soc 2001, 123, 9, 1862.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(XXV)	47049	tert-butyl (1S,2R,19R,22R,34S,37R,40R,52S)-15-amino-5-chloro-2-hydroxy-26,31,44,47,49,66-hexamethoxy-52-(((2-methoxyethoxy)methoxy)methyl)-21,35,38,54,56,58-hexaoxo-7,13,28-trioxa-20,36,39,53,55,57-hexaazaundecacyclo[38.14.2.2(3,6).2(14,17).2(19,34).1(8,12).1(23,27).1(29,33).1(41,45).0(10,37).0(46,51)]hexahexaconta-3,5,8(66),9,11,14,16,23(65),24,26,29(carbamate		C₇₃H₇₇ClN₈O₂₁	详情	详情
(XXVI)	47050	tert-butyl (1S,2R,19R,22R,34S,37R,40R,52S)-5,15-dichloro-2-hydroxy-26,31,44,47,49,66-hexamethoxy-52-(((2-methoxyethoxy)methoxy)methyl)-21,35,38,54,56,58-hexaoxo-7,13,28-trioxa-20,36,39,53,55,57-hexaazaundecacyclo[38.14.2.2(3,6).2(14,17).2(19,34).1(8,12).1(23,27).1(29,33).1(41,45).0(10,37).0(46,51)]hexahexaconta-3,5,8(66),9,11,14,16,23(65),24,26,29(carbamate		C₇₃H₇₅Cl₂N₇O₂₁	详情	详情
(XXVII)	40582			C₇₉H₈₉Cl₂N₇O₂₁Si	详情	详情
(XXVIII)	42057	2-Bromo-1,3,2-benzodioxaborole; B-Bromocatecholborane	51901-85-0	C₆H₄BBrO₂	详情	详情
(XXIX)	40583			C₇₅H₈₁Cl₂N₇O₁₉Si	详情	详情
(XXX)	40584			C₇₅H₇₉Cl₂N₇O₂₀Si	详情	详情

合成路线2

该中间体在本合成路线中的序号：(XVII)

Elimination of the Mem protecting group of (XVI) by treatment with borane (XVII) gives the primary alcohol (XVIII), which is oxidated to the corresponding acid with DMP and NaClO2 and simultaneously methylated with Tms-CHN2 to yield the methyl ester (XIX). The controlled hydrolysis of the cyano group of (XIX) with H2O2 and K2CO3 affords the corresponding amide (XX), which is finally desilylated with TBAF and demethylated with AlBr3 to furnish the target aglycon.

参考文献中间体

合成目标

【1】 Boger, D.L.; et al.; Diasteroselective total synthesis of the vancomycin aglycon with ordered atropisomer equilibrations. J Am Chem Soc 1999, 121, 13, 3226.
【2】 Boger, D.L.; et al.; Total synthesis of the vancomycin aglycon. J Am Chem Soc 1999, 121, 43, 10004.

中间体序号	中间体编号	品名	CAS号	分子式	供应商	用于合成
(XVI)	42056	tert-butyl (1R)-1-([[(1S,2R,18R,19R,22S,25R,28R,40S)-2,18-bis[[tert-butyl(dimethyl)silyl]oxy]-5,15-dichloro-22-(cyanomethyl)-32,35,37,50-tetramethoxy-40-[[(2-methoxyethoxy)methoxy]methyl]-20,23,26,42,44-pentaoxo-7,13-dioxa-21,24,27,41,43-pentaazaoct		C₇₈H₁₀₄Cl₂N₈O₁₉Si₂	详情	详情
(XVII)	42057	2-Bromo-1,3,2-benzodioxaborole; B-Bromocatecholborane	51901-85-0	C₆H₄BBrO₂	详情	详情
(XVIII)	42058	tert-butyl (1R)-1-([[(1S,2R,18R,19R,22S,25R,28R,40S)-2,18-bis[[tert-butyl(dimethyl)silyl]oxy]-5,15-dichloro-22-(cyanomethyl)-40-(hydroxymethyl)-32,35,37,50-tetramethoxy-20,23,26,42,44-pentaoxo-7,13-dioxa-21,24,27,41,43-pentaazaoctacyclo[26.14.2.2(3,		C₇₄H₉₆Cl₂N₈O₁₇Si₂	详情	详情
(XIX)	42059	methyl (1S,2R,18R,19R,22S,25R,28R,40S)-19-([(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl]amino)-2,18-bis[[tert-butyl(dimethyl)silyl]oxy]-5,15-dichloro-22-(cyanomethyl)-32,35,37,50-tetramethoxy-20,23,26,42,44-pentaoxo-7,13-dioxa-21,2		C₇₅H₉₆Cl₂N₈O₁₈Si₂	详情	详情
(XX)	42060	methyl (1S,2R,18R,19R,22S,25R,28R,40S)-22-(2-amino-2-oxoethyl)-19-([(2R)-2-[(tert-butoxycarbonyl)(methyl)amino]-4-methylpentanoyl]amino)-2,18-bis[[tert-butyl(dimethyl)silyl]oxy]-5,15-dichloro-32,35,37,50-tetramethoxy-20,23,26,42,44-pentaoxo-7,13-dio		C₇₅H₉₈Cl₂N₈O₁₉Si₂	详情	详情

Extended Information