(1R,2R,5R,6S)-5-bromo-6-hydroxycyclohex-3-ene-1,2,3-trimethyl triacetate | 233664-00-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,2R,5R,6S)-5-bromo-6-hydroxycyclohex-3-ene-1,2,3-trimethyl triacetate
• 英文别名: [(1R,2R,5R,6S)-2,3-bis(acetyloxymethyl)-5-bromo-6-hydroxycyclohex-3-en-1-yl]methyl acetate
• CAS: 233664-00-1
• 化学式: C₁₅H₂₁BrO₇
• 分子量: 393.232
• InChiKey: GKXADHOMFZKBGX-XQLPTFJDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  99.1
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (1R,2R,5R,6S)-5-bromo-6-hydroxycyclohex-3-ene-1,2,3-trimethyl triacetate 在 sodium sulfide 、 氨 、 三乙胺 、 tetramethylguanidinum azide 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 26.08h， 生成 (1R,2R,5S,6S)-5-amino-6-hydroxycyclohex-3-ene-1,2,3-trimethanol
  参考文献：
  名称：

  Total Asymmetric Synthesis of Doubly Branched Carba-hexopyranoses and Amino Derivatives Starting from theDiels-Alder Adducts of Maleic Anhydride to Furfuryl Esters

  摘要：

  The Diels-Alder adducts of maleic anhydride to furfuryl esters were reduced into 7-oxabicyclo[2.2.l]hept-5-ene-1.2-exo,3-exo-trimethanol (+/-)-15 and enantiomerically pure (-)-15 (Scheme 1). The tripivalate of (+/-)-15 was converted into (1RS,2RS,3RS,4RS,5SR,6SR)-1,5,6-tris(hydroxymethyl)cyclohexane-1,2,3,4-tetrol ((+/-)-23; Scheme 2). Reaction of BBr3 with the triacetate (+/-)-30 of (+/-)-15 gave (1RS,2RS,5RS,6RS)-5-bromo-6-hydroxycyclohex-3-ene-1,2,3-trimethyl triacetate ((+/-)-31) at -78 degrees, and (1RS,2RS,5SR,8SR)-2-endo-hydroxy-6-oxabicylo[3.2.l]oct-3-ene-5,8-dimethyl diacetate ((+/-)-32) at 0 degrees (Scheme 3). Single-crystal X-ray diffraction of (1RS,2RS,5SR,8SR)-2-acetoxy-6-oxabicyclo[3.2.1]oct-3-ene-5,8-dimethyl diacetate ((+/-)-33) was carried out. Displacement of bromide (+)-31 (derived from (-)-15) with azide anion gave (+)-38 which was transformed into (+)-( 1R,2R,5S,6S)-5-amino-6-hydroxycyclohex-3-ene-1,2,3-trimethanol ((+)-40) (Scheme 4). Reaction of (+/-)-31 with BBr3 at 0 degrees, followed by azide disubstitution led to (1RS,2RS,5SR,6SR)-5-amino-3-(aminomethyl)-6-hydroxycyclohex-3-ene-1,2-dimethanol ((+/-)-45). Dihydroxylation of (+/-)-38 and further transformations gave (1RS,2RS,3SR,4RS,5SR,6RS)-5-amino-1,4,6-trihydroxycyclohexane-1,2,3-trimethanol ((+/-)-49) and (1RS,2RS, 3SR,4RS,5SR,6RS)-2,3-dihydroxy-7-oxabicyclo[4.1.0]heptane-2,3,4-trimethanol ((+/-)-55) (Schemes 5 and 6). Expoxidation of the 4-nitrobenzoate (+/-)-61 of (+/-)-38 allowed the preparation of (1RS,2RS,3SR,4RS,5RS)-5-amino-4-amino-1.4-dihydroxycyclohexane-1,2,3-trimethanol ((+)-65) and of (1RS,2RS,3SR,4RS,5SR,6RS)-5-amino-4-hydroxy-7-oxabicyclo[4.1.0]heptane-1,2,3 ((+/-)-67) (Scheme 7). The new unprotected polyols and aminopolyols were tested for their inhibitory activity toward commercially available glycohydrolases. At 1 mM concentration, 34, 30, and 31% inhibition of beta-galactosidase from bovine liver was observed for (+/-)-40, (+/-)-65, and (1)-67, respectively.

  DOI：

  10.1002/(sici)1522-2675(19990609)82:6<821::aid-hlca821>3.0.co;2-k
• 作为产物：
  描述：

  7-oxabicyclo<2.2.1>hept-5-ene-1,2-exo,3-exo-trimethyl triacetate 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以95%的产率得到(1R,2R,5R,6S)-5-bromo-6-hydroxycyclohex-3-ene-1,2,3-trimethyl triacetate
  参考文献：
  名称：

  Total Asymmetric Synthesis of Doubly Branched Carba-hexopyranoses and Amino Derivatives Starting from theDiels-Alder Adducts of Maleic Anhydride to Furfuryl Esters

  摘要：

  The Diels-Alder adducts of maleic anhydride to furfuryl esters were reduced into 7-oxabicyclo[2.2.l]hept-5-ene-1.2-exo,3-exo-trimethanol (+/-)-15 and enantiomerically pure (-)-15 (Scheme 1). The tripivalate of (+/-)-15 was converted into (1RS,2RS,3RS,4RS,5SR,6SR)-1,5,6-tris(hydroxymethyl)cyclohexane-1,2,3,4-tetrol ((+/-)-23; Scheme 2). Reaction of BBr3 with the triacetate (+/-)-30 of (+/-)-15 gave (1RS,2RS,5RS,6RS)-5-bromo-6-hydroxycyclohex-3-ene-1,2,3-trimethyl triacetate ((+/-)-31) at -78 degrees, and (1RS,2RS,5SR,8SR)-2-endo-hydroxy-6-oxabicylo[3.2.l]oct-3-ene-5,8-dimethyl diacetate ((+/-)-32) at 0 degrees (Scheme 3). Single-crystal X-ray diffraction of (1RS,2RS,5SR,8SR)-2-acetoxy-6-oxabicyclo[3.2.1]oct-3-ene-5,8-dimethyl diacetate ((+/-)-33) was carried out. Displacement of bromide (+)-31 (derived from (-)-15) with azide anion gave (+)-38 which was transformed into (+)-( 1R,2R,5S,6S)-5-amino-6-hydroxycyclohex-3-ene-1,2,3-trimethanol ((+)-40) (Scheme 4). Reaction of (+/-)-31 with BBr3 at 0 degrees, followed by azide disubstitution led to (1RS,2RS,5SR,6SR)-5-amino-3-(aminomethyl)-6-hydroxycyclohex-3-ene-1,2-dimethanol ((+/-)-45). Dihydroxylation of (+/-)-38 and further transformations gave (1RS,2RS,3SR,4RS,5SR,6RS)-5-amino-1,4,6-trihydroxycyclohexane-1,2,3-trimethanol ((+/-)-49) and (1RS,2RS, 3SR,4RS,5SR,6RS)-2,3-dihydroxy-7-oxabicyclo[4.1.0]heptane-2,3,4-trimethanol ((+/-)-55) (Schemes 5 and 6). Expoxidation of the 4-nitrobenzoate (+/-)-61 of (+/-)-38 allowed the preparation of (1RS,2RS,3SR,4RS,5RS)-5-amino-4-amino-1.4-dihydroxycyclohexane-1,2,3-trimethanol ((+)-65) and of (1RS,2RS,3SR,4RS,5SR,6RS)-5-amino-4-hydroxy-7-oxabicyclo[4.1.0]heptane-1,2,3 ((+/-)-67) (Scheme 7). The new unprotected polyols and aminopolyols were tested for their inhibitory activity toward commercially available glycohydrolases. At 1 mM concentration, 34, 30, and 31% inhibition of beta-galactosidase from bovine liver was observed for (+/-)-40, (+/-)-65, and (1)-67, respectively.

  DOI：

  10.1002/(sici)1522-2675(19990609)82:6<821::aid-hlca821>3.0.co;2-k