(1R,2R,3S)-3-O-Benzyl-5-benzyloxymethyl-1,2-O-cyclohexylidene-cyclohex-4-en-1,2,3-triol | 135735-90-9

• 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: (1R,2R,3S)-3-O-Benzyl-5-benzyloxymethyl-1,2-O-cyclohexylidene-cyclohex-4-en-1,2,3-triol
• 英文别名: (3aR,4S,7aR)-4-phenylmethoxy-6-(phenylmethoxymethyl)spiro[3a,4,7,7a-tetrahydro-1,3-benzodioxole-2,1'-cyclohexane]
• CAS: 135735-90-9
• 化学式: C₂₇H₃₂O₄
• 分子量: 420.549
• InChiKey: HTPIGEJHGPHCIL-NXCFDTQHSA-N

物化性质

• 沸点：
  546.0±50.0 °C(predicted)
• 密度：
  1.17±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2R,3S)-3-O-Benzyl-5-benzyloxymethyl-1,2-O-cyclohexylidene-cyclohex-4-en-1,2,3-triol 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 双氧水 、 N,N'-硫羰基二咪唑 、 三氟乙酸 、 三甲氧基磷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 4-O-acetyl-1,5-anhydro-3,6-di-O-benzyl-2-deoxy-5a-carba-D-arabino-hex-1-enitol
  参考文献：
  名称：

  Facile syntheses of pseudo-α-D-glucopyranose and pseudo-α-D-mannopyranose

  摘要：

  假δ±-D-吡喃葡萄糖 1 和假δ±-D-吡喃甘露糖 2 分别是通过烯 8 的顺式和反式立体选择性羟基化反应得到的，烯 8 很容易从(â)-奎宁酸中得到。

  DOI：

  10.1039/c39910000756
• 作为产物：
  描述：

  (1R,2R,3S)-1,2-O-Cyclohexylidene-5-hydroxymethyl-4-cyclohexen-1,2,3-triol 、 溴甲苯 在 四丁基碘化铵 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以72%的产率得到(1R,2R,3S)-3-O-Benzyl-5-benzyloxymethyl-1,2-O-cyclohexylidene-cyclohex-4-en-1,2,3-triol
  参考文献：
  名称：

  Facile syntheses of pseudo-α-D-glucopyranose and pseudo-α-D-mannopyranose

  摘要：

  假δ±-D-吡喃葡萄糖 1 和假δ±-D-吡喃甘露糖 2 分别是通过烯 8 的顺式和反式立体选择性羟基化反应得到的，烯 8 很容易从(â)-奎宁酸中得到。

  DOI：

  10.1039/c39910000756

文献信息

• Expeditious Synthesis of Tri- and Tetrahydroxyazepanes from <scp>d</scp>-(−)-Quinic Acid as Potent Glycosidase Inhibitors
  作者：Tzenge-Lien Shih、Ru-Ying Yang、Shiou-Ting Li、Cheng-Fan Chiang、Chun-Hung Lin

  DOI：10.1021/jo070058x

  日期：2007.5.1

  Several new stereoisomers of 3,4,6-trihydroxyazepanes and 7-hydroxymethyl-3,4,5-trihydroxyazepanes as well as known 3,4,5-trihydroxyazepanes were synthesized as potent glycosidase inhibitors from d-(−)-quinic acid in an efficient manner. The key step employs dihydroxylation of protected chiral 1,4,5-cyclohex-2-enetriols under RuCl3/NaIO4/phosphate buffer (pH 7) condition, followed by reductive amino cyclization

  由d -（-）-奎宁酸合成了3,4,6-三羟基氮杂环庚烷和7-羟甲基-3,4,5-三羟基氮杂环庚烷以及已知的3,4,5-三羟基氮杂环庚烷作为强大的糖苷酶抑制剂。一种有效的方式。关键步骤是在RuCl 3 / NaIO 4 /磷酸盐缓冲液（pH 7）条件下，将受保护的手性1,4,5-环己-2-烯三醇进行二羟基化，然后进行还原性氨基环化反应。我们发现选择合适的手性1,4,5-环己-2-烯三醇的C1-OH保护基会增加环化的收率。初步的生物学数据表明，其中某些氮杂环丙烷对α-甘露糖苷酶和α-岩藻糖苷酶具有有效的抑制作用。
• Facile syntheses of pseudo-α-<scp>D</scp>-glucopyranose and pseudo-α-<scp>D</scp>-mannopyranose
  作者：Tony K. M. Shing、Yu-xin Cui、Ying Tang

  DOI：10.1039/c39910000756

  日期：——

  Pseudo-α-D-glucopyranose 1 and pseudo-α-D-mannopyranose 2 are obtained via a stereoselective cis- and trans-hydroxylation respectively of the alkene 8, which is readily derived from (–)-quinic acid.

  假δ±-D-吡喃葡萄糖 1 和假δ±-D-吡喃甘露糖 2 分别是通过烯 8 的顺式和反式立体选择性羟基化反应得到的，烯 8 很容易从(â)-奎宁酸中得到。
• The first synthesis of 7-(hydroxymethyl)thiepane-3,4,5-triols from d-(−)-quinic acid
  作者：Tzenge-Lien Shih、Wei-Lin Gao

  DOI：10.1016/j.tet.2012.12.047

  日期：2013.2

  Seven thiepanes, the seven-membered-ring thiosugars, were first synthesized in 11–12 steps starting from d-(−)-quinic acid. Each thiepane is unique for its flexible conformation with a hydroxymethyl group at its C7 position. The key step was the deprotection of ether groups in compounds 7, 8, and 18–21 by 1.0 M BCl3 of CH2Cl2 solution at −78 °C to lead to the corresponding thiepanes. These target molecules

  从d -（-）-奎尼酸开始，首先以11–12步合成了七个七烷，即七元环的硫糖。每个硫烷因其在C7位置具有羟甲基的柔性构象而独特。的关键步骤是化合物中的醚基团的脱保护7，8，和18 - 21通过的1.0M的BCl 3的CH 2氯2溶液在-78℃下将导致相应的thiepanes。这些靶分子均显示出与我们先前的报告完全一致的扭曲椅构象。
• Facile Syntheses of Valiolamine and Its Diastereomers from (−)-Quinic Acid.¹ Nucleophilic Substitution Reactions of 5-(Hydroxymethyl)cyclohexane-1,2,3,4,5-pentol
  作者：Tony K. M. Shing、Leong H. Wan

  DOI：10.1021/jo9607828

  日期：1996.1.1

  Valiolamine (1), 1-epi-valiolamine (2), 2-epi-valiolamine (3), (1R,2R)-valiolamine (4), and 2-amino regioisomer 17 have been prepared from (-)-quinic acid (6) in 14 (8.4% overall yield), 13 (9.0%), 15 (4.3%), 17 steps (2.5%), and 12 steps (13%), respectively. Charged nucleophilic ring-openings of cyclic sulfate (1R,2S,3S,4S,5S)-4,5-di-O-acetyl-3-O-benzyl-5-(benzyloxymethyl)-1,2-O,O-sulfonyl-cyclohexane-1,2,3,4,5-pentol (11) occurred regioselectively at C-2, whereas the corresponding ring-openings of its (1S,2R)-diastereomer 34 proceeded preponderantly at C-1. (1R,2S,3R,4S,5S)-2,4,5-Tri-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)-1-O-(trifluoromethanesulfonyl) cyclohexane-1,2,3,4,5-pentol (24) underwent novel internal displacement spontaneously to form (1S,2S,3R,4S,5S)-1,2,4-tri-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)cyclohexane-1,2,3,4,5-pentol (25), whereas its 2-epimer was inert under the same conditions. Ruthenium-catalyzed dihydroxylation of alkene, (3R,4S,5S)-4,5-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)-1-cyclohexene-3,4,5-triol (31), gave the desired beta-1,2-diol 32 in higher yield and stereoselectivity than the osmium tetraoxide protocol. The regioselectivity of charged nucleophilic ring-openings of cyclic sulfates 11, 34, and 38 is discussed.
• Shing, Tony K. M.; Wan, Leong H., Angewandte Chemie, 1995, vol. 107, # 15, p. 1742 - 1744
  作者：Shing, Tony K. M.、Wan, Leong H.

  DOI：——

  日期：——