1,3:4,6-di-O-benzylidene-2,5-di-O-methanesulfonyl-D-mannitol | 28224-74-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 1,3:4,6-di-O-benzylidene-2,5-di-O-methanesulfonyl-D-mannitol
• 英文别名: 1,3:4,6-Di-O-benzyliden-2,5-di-O-methylsulfonyl-D-mannitol；[(4S,5R)-4-[(4S,5R)-5-methylsulfonyloxy-2-phenyl-1,3-dioxan-4-yl]-2-phenyl-1,3-dioxan-5-yl] methanesulfonate
• CAS: 28224-74-0
• 化学式: C₂₂H₂₆O₁₀S₂
• 分子量: 514.574
• InChiKey: YGOPSNHHGKAASZ-ZHEILYIOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  140
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,3:4,6-di-O-benzylidene-2,5-di-O-methanesulfonyl-D-mannitol 在 三乙胺 、 肼 作用下， 以 二氯甲烷 、 异丙醇 为溶剂， 反应 74.0h， 生成 N-[(1R,2R,7S,9S)-4,12-diphenyl-3,5,11,13-tetraoxa-8-azatricyclo[7.4.0.02,7]tridecan-8-yl]methanimine
  参考文献：
  名称：

  N，N-二烷基hydr与烯酮之间的立体选择性[2 + 2]环加成反应的研究。

  摘要：

  手性，非外消旋的N，N-二烷基alkyl唑酮1和官能化的烯酮之间的类Staudinger样环加成反应构成了β-内酰胺环立体选择性构建的有效方法。强调了二烷基氨基辅助结构的微调潜力，释放游离氮杂环丁酮的高产脱保护方法的可用性以及作为N-二烷基氨基亚胺的high的高热稳定性和化学稳定性，是其关键要素。该策略的成功。关于通用性，这最后一个方面特别重要：甚至来自易于烯化的醛或甲醛的也反应生成相应的具有高化学和立体化学收率的环加合物。β-氨基-α-羟酸（2R，3S）-苯基异丝氨酸（42）和（2R，作为该程序的合成效用的说明性实例，完成了3S）-去甲他汀（45）的制备。通过从头算的方法研究了g系列助剂的环加成模型系统。收集到的结果通过两性离子中间体支持了两步机理，并根据the的Re面的优选向外环加成解释了观察到的绝对和相对立体化学。

  DOI：

  10.1002/chem.200400452
• 作为产物：
  描述：

  甘露醇 在 硫酸 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 76.0h， 生成 1,3:4,6-di-O-benzylidene-2,5-di-O-methanesulfonyl-D-mannitol
  参考文献：
  名称：

  Synthesis of amphiphilic polyhydroxylated pyrrolidines as potential glycosidase inhibitors

  摘要：

  Several polyhydroxylated pyrrolidines with an aliphatic long chain on the ring nitrogen were prepared starting from D-mannitol. An amphiphilic bis-azasugar scaffold has been also prepared. These products behave as cationic surfactants and show a promising anti HIV-I activity. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01361-6

文献信息

• Synthesis of new analogues of salacinol containing a pendant hydroxymethyl group as potential glycosidase inhibitors
  作者：Ravindranath Nasi、B. Mario Pinto

  DOI：10.1016/j.carres.2006.06.022

  日期：2006.10

  The synthesis of new analogues of the naturally occurring glycosidase inhibitor, salacinol, and its ammonium analogue, ghavamiol is described. These analogues contain an additional hydroxymethyl group at C-1, which was intended to form additional polar contacts within the active site of glycosidase enzymes. The target zwitterionic compounds were synthesized by means of nucleophilic attack at the least

  描述了天然存在的糖苷酶抑制剂新的类似物salacinol及其铵类似物ghavamiol的合成。这些类似物在C-1处包含一个额外的羟甲基，旨在在糖苷酶的活性位点内形成额外的极性接触。目标两性离子化合物是通过亲核攻击在2,4-O-亚苄基-1-（或d）-赤藓糖醇1,3-环硫酸盐的受阻最少的碳原子上由2,5-脱水-1,3合成的： 4,6-二-O-亚苄基-2,5-二脱氧-5-硫代（或1,5-亚氨基）-1-ID醇。
• Short-step synthesis of chiral C2-symmetric 2,3,4,5-tetrasubstituted pyrrolidines from D-mannitol and their use as chiral ligands in the reaction of diethylzinc and benzaldehyde
  作者：Yukio Masaki、Hirohisa Oda、Kenichi Kazuta、Akira Usui、Akichika Itoh、Fang Xu

  DOI：10.1016/s0040-4039(00)61197-8

  日期：1992.8

  rolidine and related chiral C2-Symmetric pyrrolidines including D2-symmetric 1,2-bis(1-pyrrolidino)-ethanes and N-hydroxyethylpyrrolidines were synthesized highly practically from D-mannitol and a high chiral induction of 82% ee was observed in investigation of efficiency of these amines as chiral catalyst ligands in the addition reaction of diethylzinc to benzaldehyde.

  （3R，4R）-双（羟基）-（2S，5S）-双（羟甲基）-吡咯烷和相关的手性C 2-对称吡咯烷，包括D 2-对称的1，2-双（1-吡咯烷）。 -乙烷和N-羟乙基吡咯烷实际上是由D-甘露糖醇合成的，在研究这些胺作为手性催化剂配体在二乙基锌与苯甲醛加成反应中的效率方面，观察到82％ee的高手性诱导。
• Regioselective oxidative cleavage of benzylidene acetals: synthesis of highly functionalized chiral intermediates
  作者：Pon Minor Senthilkumar、Appu Aravind、Sundarababu Baskaran

  DOI：10.1016/j.tetlet.2006.12.078

  日期：2007.2

  A mild and efficient method for the regioselective oxidative cleavage of benzylidene acetals with KBrO3/Na2S2O4 under bi-phasic conditions (EtOAc/H2O), leading to highly functionalized chiral intermediates, is reported.

  报道了在两相条件下（EtOAc / H 2 O）用KBrO 3 / Na 2 S 2 O 4进行亚苄基乙缩醛的区域选择性氧化裂解的温和有效方法，导致高度官能化的手性中间体。
• Synthesis of C 2 -symmetric guanidino-sugars as potent inhibitors of glycosidases
  作者：Yves Le Merrer、Laurence Gauzy、Christine Gravier-Pelletier、Jean-Claude Depezay

  DOI：10.1016/s0968-0896(99)00294-1

  日期：2000.2

  A series of enantiomerically pure C-2-Symmetric guanidino-sugars was synthesized from D-mannitol. The first method described involves direct opening of a bis-epoxide by guanidine, whereas the second one deals with a mercury-catalyzed transformation of a cyclic thiourea into a N,N,N"-trisubstituted guanidine as a key step. The biological activity of these compounds towards several glycosidases has been evaluated. One of them (5) was found to selectively inhibit alpha-L-fucosidase of bovin kidney (2.8 mu M). (C) 2000 Elsevier Science Ltd. All rights reserved.
• Regioselective cleavage of the bis-benzylidene acetal of d-mannitol under oxidative and reductive conditions: a new approach to C2-symmetric chiral ligands
  作者：Appu Aravind、Subhendu K. Mohanty、T. Veerabhadra Pratap、Sundarababu Baskaran

  DOI：10.1016/j.tetlet.2005.03.038

  日期：2005.4

  A highly regioselective oxidative cleavage of 1,3:4,6-di-O-benzylidene-D-mannitol was carried out using NBS and the resultant product was readily converted to the Q-symmetric chiral ligand, (R,R)-3,4-dihydroxy-1,5-hexadiene. On the other hand, reductive cleavage of 1,3:4,6-di-O-benzylidene-D-mannitol was achieved in a highly regioselective manner using BF(3)center dot OEt2 and Et3SiH to give a highly functionalized benzyl ether, which was converted to a synthetically useful C-2-symmetric bis-amino alcohol derivative. (c) 2005 Elsevier Ltd. All rights reserved.