tert-butyl (3aR,4S,7R,7aS)-2,2-dimethyl-5-[(4-methylphenyl)sulfonyl]-3a,4,7,7a-tetrahydro-4,7-epimino-1,3-benzodioxole-8-carboxylate | 205813-79-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tert-butyl (3aR,4S,7R,7aS)-2,2-dimethyl-5-[(4-methylphenyl)sulfonyl]-3a,4,7,7a-tetrahydro-4,7-epimino-1,3-benzodioxole-8-carboxylate
• 英文别名: (+)-(1S,2R,3S,4R)-7-tert-butoxycarbonyl-6-p-toluenesulfonyl-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]hept-5-ene；tert-butyl (1S,2S,6R,7S)-4,4-dimethyl-8-(4-methylphenyl)sulfonyl-3,5-dioxa-10-azatricyclo[5.2.1.02,6]dec-8-ene-10-carboxylate
• CAS: 205813-79-2
• 化学式: C₂₁H₂₇NO₆S
• 分子量: 421.514
• InChiKey: XLXIAGAUZPEPOS-XOYOTBSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  90.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tert-butyl (3aR,4S,7R,7aS)-2,2-dimethyl-5-[(4-methylphenyl)sulfonyl]-3a,4,7,7a-tetrahydro-4,7-epimino-1,3-benzodioxole-8-carboxylate 在 吡啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 disodium hydrogenphosphate 、 sodium amalgam 、 正丁基锂 、 双氧水 、 碳酸氢钠 、 对甲苯磺酸 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 60.75h， 生成 [(1R,4S,5S,6R)-5,6-diacetyloxy-4-[(2-methylpropan-2-yl)oxycarbonylamino]cyclohex-2-en-1-yl] acetate
  参考文献：
  名称：

  Synthesis of Conduramines from N-tert-Butoxycarbonylpyrrole

  摘要：

  Two related synthetic strategies were devised to convert the Diels-Alder adduct 3c of Boc-pyrrole and p-toluenesulfonylacetylene into various racemic and optically pure conduramines. One process consists of the regio-and stereoselective hydroxylation of 3c to the tri-and dihydroxylated azabicyclo[2.2.1]heptane derivatives 10b (Scheme 2) and the exo-endo mixture 13-14 (Scheme 3). Anionic fragmentation of 10b (methylmagnesium bromide) and of the 13-14 sulfone mixture (lithium bis(trimethylsilyl)amide) generated the corresponding tri-and dihydroxylated aminocyclohexenes 17 and 16 (Scheme 3). Compound 17 is an aminocyclitol with a stereochemistry and partial aminotriol sequence identical to that found in neoinosamine. Compound 16 served as a source of the protected and fi ee aminodiols 35b, and 35a (Scheme 6), which were stereospecifically epoxidized to 36 (Scheme 6) and 40 (Scheme 7). Phenylselenide cleavage of these epoxides provided 37 (Scheme 6) and 41a (Scheme 7), which after selenoxide cycloelimination and protecting group manipulation were converted into (+/-)-conduramine C-l (39a, Scheme 6) and the previously unreported, all-cis-conduramine D-l (43a, Scheme 7). In a second process, anionic fragmentaion of the bicyclic system is effected prior to introduction of the hydroxyl groups, as exemplified by the high-yielding conversion of the exo-endo mixture of azabicycloheptenes 11 and 12 into the aminocyclohexadiene 15 (Scheme 3). Osmate catalyzed cis-dihydroxylation of the derived bis-Boc derivative 20 (Scheme 4) Zed stereospecifically to the alpha-cis-diol 21 which was transformed into (+/-)-conduramine A-1 (27a) and its tetraacetyl derivative 27b via the epoxy compound 24. On the other hand, peracid oxidation of the diene 15 gave the beta-epoxide 28 (Scheme 5) which was cleaved to the trans-diol 29 with aqueous sulfuric acid. This diol was converted into (+/-)-conduramine F-1(34a) and its tetraacetyl derivative (34b) by a reaction sequence similar to that used for the other conduramine syntheses. Fractional crystallization of the diastereomeric mixture of Michael adducts obtained from (+/-)-3c and (-)methyl lactate gave (-)-44a and (-)-45a both in greater than or equal to 47% yield (Scheme 8). Both the carboxylic acid (+)-44b and the primary alcohol (+)-46 derived from (-)-44a were converted into (-)-3c with excess methylmagnesium bromide (ca. 40% overall yield). In the same way (-)-45a was transformed into optically pure (+)-3c. (-)-3c and (+)-3c were then converted into (-)-conduramine C-l [(-)-39a] and (+)-conduramine D-l [(+)-43a] by procedures identical to those used for the racemic compounds.

  DOI：

  10.1021/jo971907r
• 作为产物：
  描述：

  1-吡咯甲酸叔丁酯 在 sodium hydroxide 、 四氧化锇 、 N-甲基吲哚酮 、 甲基溴化镁 、 sodium hydride 、 碳酸氢钠 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 水 、 丙酮 、 甲苯 、 叔丁醇 为溶剂， 反应 75.08h， 生成 tert-butyl (3aR,4S,7R,7aS)-2,2-dimethyl-5-[(4-methylphenyl)sulfonyl]-3a,4,7,7a-tetrahydro-4,7-epimino-1,3-benzodioxole-8-carboxylate
  参考文献：
  名称：

  Synthesis of Conduramines from N-tert-Butoxycarbonylpyrrole

  摘要：

  Two related synthetic strategies were devised to convert the Diels-Alder adduct 3c of Boc-pyrrole and p-toluenesulfonylacetylene into various racemic and optically pure conduramines. One process consists of the regio-and stereoselective hydroxylation of 3c to the tri-and dihydroxylated azabicyclo[2.2.1]heptane derivatives 10b (Scheme 2) and the exo-endo mixture 13-14 (Scheme 3). Anionic fragmentation of 10b (methylmagnesium bromide) and of the 13-14 sulfone mixture (lithium bis(trimethylsilyl)amide) generated the corresponding tri-and dihydroxylated aminocyclohexenes 17 and 16 (Scheme 3). Compound 17 is an aminocyclitol with a stereochemistry and partial aminotriol sequence identical to that found in neoinosamine. Compound 16 served as a source of the protected and fi ee aminodiols 35b, and 35a (Scheme 6), which were stereospecifically epoxidized to 36 (Scheme 6) and 40 (Scheme 7). Phenylselenide cleavage of these epoxides provided 37 (Scheme 6) and 41a (Scheme 7), which after selenoxide cycloelimination and protecting group manipulation were converted into (+/-)-conduramine C-l (39a, Scheme 6) and the previously unreported, all-cis-conduramine D-l (43a, Scheme 7). In a second process, anionic fragmentaion of the bicyclic system is effected prior to introduction of the hydroxyl groups, as exemplified by the high-yielding conversion of the exo-endo mixture of azabicycloheptenes 11 and 12 into the aminocyclohexadiene 15 (Scheme 3). Osmate catalyzed cis-dihydroxylation of the derived bis-Boc derivative 20 (Scheme 4) Zed stereospecifically to the alpha-cis-diol 21 which was transformed into (+/-)-conduramine A-1 (27a) and its tetraacetyl derivative 27b via the epoxy compound 24. On the other hand, peracid oxidation of the diene 15 gave the beta-epoxide 28 (Scheme 5) which was cleaved to the trans-diol 29 with aqueous sulfuric acid. This diol was converted into (+/-)-conduramine F-1(34a) and its tetraacetyl derivative (34b) by a reaction sequence similar to that used for the other conduramine syntheses. Fractional crystallization of the diastereomeric mixture of Michael adducts obtained from (+/-)-3c and (-)methyl lactate gave (-)-44a and (-)-45a both in greater than or equal to 47% yield (Scheme 8). Both the carboxylic acid (+)-44b and the primary alcohol (+)-46 derived from (-)-44a were converted into (-)-3c with excess methylmagnesium bromide (ca. 40% overall yield). In the same way (-)-45a was transformed into optically pure (+)-3c. (-)-3c and (+)-3c were then converted into (-)-conduramine C-l [(-)-39a] and (+)-conduramine D-l [(+)-43a] by procedures identical to those used for the racemic compounds.

  DOI：

  10.1021/jo971907r

文献信息

• Synthesis of Enantiomerically Pure 1,2-Diamine Derivatives of 7-Azabicyclo[2.2.1]heptane. New Leads as Glycosidase Inhibitors and Rigid Scaffolds for the Preparation of Peptide Analogues
  作者：Antonio J. Moreno-Vargas、Catherine Schütz、Rosario Scopelliti、Pierre Vogel

  DOI：10.1021/jo0301088

  日期：2003.7.1

  Enantiomerically pure alcohols (-)- and (+)-7-tert-butoxycarbonyl-6-endo-p-toluenesulfonyl-7azabicyclo[2.2.1]hept-2-en-5-endo-ol ((-)-11 and (+)-11) have been obtained from the Diels-Alder adduct of N-(tert-butoxycarbonyl)pyrroel and 2-bromo-1-p-toluenesulfonylacetylene, including a resolution method. These two alcohols were converted into (+)- and (-)-5-exo-amino-7-(tertbutoxycarbonyl))-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-18 and (-)-18) and (+)and (-)-5-endo-amino-7-(tert-butoxycarbonyl)-2,3-exo-isopropylidenedioxy-7-azabicyclo[2.2.1]heptane ((+)-19 and (-)-19) after adequate fanctionalization and desulfonylation steps. The corresponding conformationally constrained bicyclic 1,2-diamines (+)-4, (-)-4, (+/-)-5, (+/-)-6, (+)-7, and (-)-7 were obtained from the protected precursors 18 and 19 and evaluated as glycosidase inhibitors. Diamines (+)-4, (-)-4, (+)-6, and (-)-6 can be seen as new nonpeptide molecular scaffolds for the design of peptide analogues.
• Synthesis of Conduramines from <i>N</i>-<i>tert</i>-Butoxycarbonylpyrrole
  作者：Regis Leung-Toung、Yanzhou Liu、Joseph M. Muchowski、Yu-Lin Wu

  DOI：10.1021/jo971907r

  日期：1998.5.1

  Two related synthetic strategies were devised to convert the Diels-Alder adduct 3c of Boc-pyrrole and p-toluenesulfonylacetylene into various racemic and optically pure conduramines. One process consists of the regio-and stereoselective hydroxylation of 3c to the tri-and dihydroxylated azabicyclo[2.2.1]heptane derivatives 10b (Scheme 2) and the exo-endo mixture 13-14 (Scheme 3). Anionic fragmentation of 10b (methylmagnesium bromide) and of the 13-14 sulfone mixture (lithium bis(trimethylsilyl)amide) generated the corresponding tri-and dihydroxylated aminocyclohexenes 17 and 16 (Scheme 3). Compound 17 is an aminocyclitol with a stereochemistry and partial aminotriol sequence identical to that found in neoinosamine. Compound 16 served as a source of the protected and fi ee aminodiols 35b, and 35a (Scheme 6), which were stereospecifically epoxidized to 36 (Scheme 6) and 40 (Scheme 7). Phenylselenide cleavage of these epoxides provided 37 (Scheme 6) and 41a (Scheme 7), which after selenoxide cycloelimination and protecting group manipulation were converted into (+/-)-conduramine C-l (39a, Scheme 6) and the previously unreported, all-cis-conduramine D-l (43a, Scheme 7). In a second process, anionic fragmentaion of the bicyclic system is effected prior to introduction of the hydroxyl groups, as exemplified by the high-yielding conversion of the exo-endo mixture of azabicycloheptenes 11 and 12 into the aminocyclohexadiene 15 (Scheme 3). Osmate catalyzed cis-dihydroxylation of the derived bis-Boc derivative 20 (Scheme 4) Zed stereospecifically to the alpha-cis-diol 21 which was transformed into (+/-)-conduramine A-1 (27a) and its tetraacetyl derivative 27b via the epoxy compound 24. On the other hand, peracid oxidation of the diene 15 gave the beta-epoxide 28 (Scheme 5) which was cleaved to the trans-diol 29 with aqueous sulfuric acid. This diol was converted into (+/-)-conduramine F-1(34a) and its tetraacetyl derivative (34b) by a reaction sequence similar to that used for the other conduramine syntheses. Fractional crystallization of the diastereomeric mixture of Michael adducts obtained from (+/-)-3c and (-)methyl lactate gave (-)-44a and (-)-45a both in greater than or equal to 47% yield (Scheme 8). Both the carboxylic acid (+)-44b and the primary alcohol (+)-46 derived from (-)-44a were converted into (-)-3c with excess methylmagnesium bromide (ca. 40% overall yield). In the same way (-)-45a was transformed into optically pure (+)-3c. (-)-3c and (+)-3c were then converted into (-)-conduramine C-l [(-)-39a] and (+)-conduramine D-l [(+)-43a] by procedures identical to those used for the racemic compounds.