4-O-<(8'S)-7'-N,6'-O-carbonyl-2',3',7'-trideoxy-8'-O-methyl-7'-(methylamino)-2'-(tosylamino)-D-glycero-α-D-allo-octodialdo-1',5':8',4'-dipyranos-1'-yl>-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine | 88970-43-8

• 分子结构分类: 有机化合物
• 英文名称: 4-O-<(8'S)-7'-N,6'-O-carbonyl-2',3',7'-trideoxy-8'-O-methyl-7'-(methylamino)-2'-(tosylamino)-D-glycero-α-D-allo-octodialdo-1',5':8',4'-dipyranos-1'-yl>-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine
• 英文别名: 4-O-[(8'S)-7'-N,6'-O-carbonyl-2',3',7'-trideoxy-8'-O-methyl-7'-(methylamino)-2'-(tosylamino)-D-glycero-α-D-allo-octodialdo-1',5':8',4'-dipyranos-1'-yl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine；N-[(3aS,4R,6S,7R,7aS)-7-[[(1S,2R,6S,7S,9S,11R,12S)-7-methoxy-5-methyl-11-[(4-methylphenyl)sulfonylamino]-4-oxo-3,8,13-trioxa-5-azatricyclo[7.4.0.02,6]tridecan-12-yl]oxy]-6-[(4-methylphenyl)sulfonylamino]spiro[3a,4,5,6,7,7a-hexahydro-1,3-benzodioxole-2,1'-cyclohexane]-4-yl]-4-methylbenzenesulfonamide
• CAS: 88970-43-8
• 化学式: C₄₄H₅₆N₄O₁₄S₃
• 分子量: 961.145
• InChiKey: FZXUUILTOPSLRY-KMAIUHRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.49
• 重原子数：
  65.0
• 可旋转键数：
  12.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  223.43
• 氢给体数：
  3.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  4-O-<(8'S)-7'-N,6'-O-carbonyl-2',3',7'-trideoxy-8'-O-methyl-7'-(methylamino)-2'-(tosylamino)-D-glycero-α-D-allo-octodialdo-1',5':8',4'-dipyranos-1'-yl>-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine 在 盐酸 作用下， 反应 72.0h， 生成 aprosamine tetrahydrochloride trihydrate
  参考文献：
  名称：

  Tatsuta, Kuniaki; Akimoto, Kohji; Takahashi, Hideaki, Tetrahedron Letters, 1983, vol. 24, # 44, p. 4867 - 4870

  摘要：

  DOI：
• 作为产物：
  描述：

  在 barium dihydroxide 、 sodium periodate 、 四氧化锇 、 sodium azide 、 ammonium cerium(IV) nitrate 、 三正丁基氢锡 、 sodium acetate 、 lithium chloride 作用下， 以 吡啶 、 乙二醇甲醚 、 二甲基亚砜 为溶剂， 反应 92.92h， 生成 4-O-<(8'S)-7'-N,6'-O-carbonyl-2',3',7'-trideoxy-8'-O-methyl-7'-(methylamino)-2'-(tosylamino)-D-glycero-α-D-allo-octodialdo-1',5':8',4'-dipyranos-1'-yl>-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine
  参考文献：
  名称：

  Tatsuta, Kuniaki; Akimoto, Kohji; Takahashi, Hideaki, Tetrahedron Letters, 1983, vol. 24, # 44, p. 4867 - 4870

  摘要：

  DOI：

文献信息

• Total Synthesis of Aminoglycoside Antibiotics, Apramycin and Saccharocin (KA-5685)
  作者：Kuniaki Tatsuta、Kohji Akimoto、Hideaki Takahashi、Takao Hamatsu、Masahiko Annaka、Mitsuhiro Kinoshita

  DOI：10.1246/bcsj.57.529

  日期：1984.2

  Apramycin and saccharocin (KA-5685) have been synthesized from previously synthesized neamine (3). Addition of allylmagnesium chloride to 4-O-[3′,4′-O-cyclohexylidene-2′-deoxy-2′-(tosylamino)-α-d-gluco-hexodialdo-1′,5′-pyranosyl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine which was derived from 3 through the 6′-N-oxide, gave 4-O-[3′,4′-O-cyclohexylidene-2′,7′,8′,9′-tetradeoxy-2′-(tosylamino)-l-glycero- and d-glycero-α-d-gluco-non-8′-enopyranosyl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamines which were in turn converted into 4-O-[(8′S)-7′-N,6′-O-carbonyl-2′,3′,7′-trideoxy-8′-O-methyl-7′-(methylamino)-2′-(tosylamino)-d-glycero-α-d-allo-octodialdo-1′,5′:8′,4′-dipyranos-1′-yl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine (25), via azidonitration of 1-N-acetyl-4-O-[3′,6′-di-O-acetyl-4′,8′-anhydro-2′,7′-dideoxy-2′-(tosylamino)-l-glycero-α-d-gluco-oct-7′-enopyranos-1′-yl]-5,6-O-cyclohexylidene-1,3-di-N-tosyl-2-deoxystreptamine and epimerization of the 6′-hydroxyl group. Successive deprotection of 25 afforded aprosamine, from which 1,2′,3,7′-tetrakis(N-benzyloxycarbonyl)aprosamine (28) was prepared, and glycosidation of 28 with 4-azido-2,3,6-tri-O-benzyl-4-deoxy-β-d-glucopyranosyl fluoride or 2,3,4,6-tetra-O-benzyl-β-d-glucopyranosyl fluoride, followed by hydrogenolysis, completed the total synthesis.

  阿普拉霉素和蔗糖霉素（KA-5685）已从先前合成的尼阿霉素（3）合成。将烯丙基氯化镁添加到4-O-[3′，4′-O-环己叉-2′-脱氧-2′-（对甲苯磺酰氨基）-α-d-葡六双醛-1′，5′-吡喃糖基]-5，6-O-环己叉-1，3-二-N-对甲苯磺酰-2-脱氧链霉胺（由3通过6′-N-氧化物衍生得到），得到4-O-[3′，4′-O-环己叉-2′，7′，8′，9′-四脱氧-2′-（对甲苯磺酰氨基）-l-甘油和d-甘油-α-d-葡-8′-烯吡喃糖基]-5，6-O-环己叉-1，3-二-N-对甲苯磺酰-2-脱氧链霉胺，后者又转化为4-O-[（8′S）-7′-N，6′-O-羰基-2′，3′，7′-三脱氧-8′-O-甲基-7′-（甲氨基）-2′-（对甲苯磺酰氨基）-d-甘油-α-d-别辛双醛-1′，5′：8′，4′-双吡喃糖基]-5，6-O-环己叉-1，3-二-N-对甲苯磺酰-2-脱氧链霉胺（25），通过1-N-乙酰基-4-O-[3′，6′-二-O-乙酰基-4′，8′-无水-2′，7′-二脱氧-2′-（对甲苯磺酰氨基）-l-甘油-α-d-葡-7′-烯吡喃糖基]-5，6-O-环己叉-1，3-二-N-对甲苯磺酰-2-脱氧链霉胺的叠氮化硝化和6′-羟基的差向异构化。25的连续脱保护得到阿普拉霉素，从中制备了1，2′，3，7′-四（N-苄氧羰基）阿普拉霉素（28），以及28与4-叠氮-2，3，6-三-O-苄基-4-脱氧-β-d-吡喃葡糖基氟或2，3，4，6-四-O-苄基-β-d-吡喃葡糖基氟的糖基化，随后进行氢解，完成了全合成。
• UMEHDZAVA, XAMAO;TAKEHUTI, KUNIAKI;TATTA, KUNIAKI
  作者：UMEHDZAVA, XAMAO、TAKEHUTI, KUNIAKI、TATTA, KUNIAKI

  DOI：——

  日期：——