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【结 构 式】

【分子编号】53368

【品名】1-(triethylsilyl)-2-propen-1-amine; 1-(triethylsilyl)-2-propenylamine

【CA登记号】n/a

【 分 子 式 】C9H21NSi

【 分 子 量 】171.35798

【元素组成】C 63.08% H 12.35% N 8.17% Si 16.39%
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 oxidation of the primary silyl ether of (XXV) with the Jones reagent gives a mixture of the carboxylic acid derivatives (XXVI) and (XXVII), which is condensed with the silylated amine (XVIII) by means of EDC and HOAT in DMF/dichloromethane to yield a mixture of the corresponding amides (XXIX) and (XXX). The rearrangement of the mixture (XXIX) + (XXX) in refluxing o-xylene affords provided a mixture of the (E)-propenylamides (XXXI) and (XXXII), which is desilylated by means of HF and pyridine in THF to give compound (XXXIII) as a diastereomeric mixture that is separated by RP-HPLC to afford the target TMC-95A.

参考文献 中间体
合成目标
【1】 Lin, S.N.; Danishefsky, S.J.; The total synthesis of proteasome inhibitors TMC-95A and TMC-95B: Discovery of a new method to generate cis-propenyl amides. Angew Chem. Int Ed 2002, 41, 3, 512.
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) 53360 N-[(10S,11R,12R,15S,18S)-15-(2-amino-2-oxoethyl)-9,14,17-trioxo-10,11,23-tris[(triethylsilyl)oxy]-12-{[(triethylsilyl)oxy]methyl}-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaen-18-yl]-3-methyl-2-oxopentanamide n/a C54H91N5O10Si4 详情 详情
(XXVI) 53361 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-23-hydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11-bis[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C42H61N5O11Si2 详情 详情
(XXVII) 53362 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11,23-tris[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C48H75N5O11Si3 详情 详情
(XXVIII) 53368 1-(triethylsilyl)-2-propen-1-amine; 1-(triethylsilyl)-2-propenylamine n/a C9H21NSi 详情 详情
(XXIX) 53363 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-23-hydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11-bis[(triethylsilyl)oxy]-N-[1-(triethylsilyl)-2-propenyl]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C51H80N6O10Si3 详情 详情
(XXX) 53364 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11,23-tris[(triethylsilyl)oxy]-N-[1-(triethylsilyl)-2-propenyl]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C57H94N6O10Si4 详情 详情
(XXXI) 53365 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-23-hydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-N-[(Z)-1-propenyl]-10,11-bis[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxilic acid n/a C45H66N6O10Si2 详情 详情
(XXXII) 53366 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-N-[(Z)-1-propenyl]-10,11,23-tris[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxamide n/a C51H80N6O10Si3 详情 详情
(XXXIII) 53367 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-10,11,23-trihydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-N-[(Z)-1-propenyl]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxamide n/a C33H38N6O10 详情 详情

合成路线2

该中间体在本合成路线中的序号：(XXVIII)

The oxidation of the primary silyl ether of (XXV) with the Jones reagent gives a mixture of the carboxylic acid derivatives (XXVI) and (XXVII). This mixture is condensed with the silylated amine (XXVIII) by means of EDC and HOAt in DMF/dichloromethane to yield a mixture of the corresponding amides (XXIX) and (XXX). The rearrangement of the mixture (XXIX) + (XXX) in refluxing o-xylene affords provided a mixture of the (E)-propenylamides (XXXI) and (XXXII), which is desilylated by means of HF and pyridine in THF to give compound (XXXIII) as a diastereomeric mixture that is separated by RP-HPLC to afford the target TMC-95B.

参考文献 中间体
合成目标
【1】 Lin, S.N.; Danishefsky, S.J.; The total synthesis of proteasome inhibitors TMC-95A and TMC-95B: Discovery of a new method to generate cis-propenyl amides. Angew Chem. Int Ed 2002, 41, 3, 512.
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) 53360 N-[(10S,11R,12R,15S,18S)-15-(2-amino-2-oxoethyl)-9,14,17-trioxo-10,11,23-tris[(triethylsilyl)oxy]-12-{[(triethylsilyl)oxy]methyl}-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaen-18-yl]-3-methyl-2-oxopentanamide n/a C54H91N5O10Si4 详情 详情
(XXVI) 53361 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-23-hydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11-bis[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C42H61N5O11Si2 详情 详情
(XXVII) 53362 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11,23-tris[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C48H75N5O11Si3 详情 详情
(XXVIII) 53368 1-(triethylsilyl)-2-propen-1-amine; 1-(triethylsilyl)-2-propenylamine n/a C9H21NSi 详情 详情
(XXIX) 53363 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-23-hydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11-bis[(triethylsilyl)oxy]-N-[1-(triethylsilyl)-2-propenyl]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C51H80N6O10Si3 详情 详情
(XXX) 53364 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-10,11,23-tris[(triethylsilyl)oxy]-N-[1-(triethylsilyl)-2-propenyl]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxylic acid n/a C57H94N6O10Si4 详情 详情
(XXXI) 53365 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-23-hydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-N-[(Z)-1-propenyl]-10,11-bis[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxilic acid n/a C45H66N6O10Si2 详情 详情
(XXXII) 53366 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-N-[(Z)-1-propenyl]-10,11,23-tris[(triethylsilyl)oxy]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxamide n/a C51H80N6O10Si3 详情 详情
(XXXIII) 53367 (10S,11R,12S,15S,18S)-15-(2-amino-2-oxoethyl)-10,11,23-trihydroxy-18-[(3-methyl-2-oxopentanoyl)amino]-9,14,17-trioxo-N-[(Z)-1-propenyl]-8,13,16-triazatetracyclo[18.3.1.0~2,7~.0~6,10~]tetracosa-1(24),2,4,6,20,22-hexaene-12-carboxamide n/a C33H38N6O10 详情 详情
Extended Information