phenoxy borane (R)-binaphthyl ester

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: phenoxy borane (R)-binaphthyl ester
• 英文别名: 13-Phenoxy-12,14-dioxa-13-borapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene
• 化学式: C₂₆H₁₇BO₃
• 分子量: 388.23
• InChiKey: PQXGCVWVCJDEIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  S-1,1'-联-2-萘酚 、 三苯基硼酸酯 以 not given 为溶剂， 生成 phenoxy borane (R)-binaphthyl ester
  参考文献：
  名称：

  手性硼酸酯-不对称合成中的通用试剂

  摘要：

  新的，轴向手性硼酸盐2，9，和11和硼酸酯3 - 6和12以良好的收率合成。它们是三种不同结构类型的代表。双环硼酸酯2和9是同手性推进剂化合物；它们的排他性形成用于提高对映体纯度1。尤其是硼酸盐是有效的路易斯酸性催化剂，可用于立体选择性Diels-Alder反应。新的七元硼化合物4，5，6，和12是用于不同不对称合成步骤的有趣试剂。活化的乙烯基硼酸酯31可以在与亚甲基环丙烷27进行[3 + 2]环加成反应中用作有效的亲环试剂，从而产生硼化的亚甲基环戊烷32。

  DOI：

  10.1016/s0022-328x(02)01323-2
• 作为试剂：
  描述：

  反-1-甲氧基-3-(三甲基硅氧基)-1,3-丁二烯 、 2-(benzylidene-amino)-3-(1H-indol-3-yl)-propionic acid methyl ester 在 phenoxy borane (R)-binaphthyl ester 作用下， 以 二氯甲烷 为溶剂， 生成 N-<(S)-2-carboxymethyl-2-(indol-3-yl)ethyl>-(6S)-2,3-didehydro-4-oxo-6-phenyl piperidine 、 N-<(S)-2-carboxymethyl-2-(indol-3-yl)ethyl>-(6R)-2,3-didehydro-4-oxo-6-phenyl piperidine
  参考文献：
  名称：

  包含育亨宾和利血平型生物碱的基本骨架的高度官能化的四环吲哚碱基的不对称合成

  摘要：

  衍生自色氨酸甲酯的席夫碱在非手性或手性硼酸酯的存在下与不同取代的富电子的甲硅烷氧基二烯反应，得到具有高非对映异构体比率（最高> 98：2）的烯胺酮5和6。通过一种新方法将这些中间体转化为高度官能化的吲哚并喹唑酮14和15，该方法采用乙烯基酰胺转化为乙烯基氯甲基胺并将其随后转化为乙烯基亚氨基酰氯作为关键步骤。

  DOI：

  10.1016/0040-4039(96)00388-7

文献信息

• Chiral boronates—versatile reagents in asymmetric synthesis
  作者：Sabine Thormeier、Bertrand Carboni、Dieter E Kaufmann

  DOI：10.1016/s0022-328x(02)01323-2

  日期：2002.9

  The new, axially chiral borates 2, 9, and 11 and boronates 3–6 and 12 are synthesized in good yields. They are representatives of three different structural types. The bicyclic borates 2 and 9 are homochiral propeller compounds; their exclusive formation is used to increase the enantiomerical purity of 1. Especially the borates are efficient Lewis acidic catalysts for stereoselective Diels–Alder reactions

  新的，轴向手性硼酸盐2，9，和11和硼酸酯3 - 6和12以良好的收率合成。它们是三种不同结构类型的代表。双环硼酸酯2和9是同手性推进剂化合物；它们的排他性形成用于提高对映体纯度1。尤其是硼酸盐是有效的路易斯酸性催化剂，可用于立体选择性Diels-Alder反应。新的七元硼化合物4，5，6，和12是用于不同不对称合成步骤的有趣试剂。活化的乙烯基硼酸酯31可以在与亚甲基环丙烷27进行[3 + 2]环加成反应中用作有效的亲环试剂，从而产生硼化的亚甲基环戊烷32。
• Synthesis and SAR studies of chiral non-racemic dexoxadrol analogues as uncompetitive NMDA receptor antagonists
  作者：Ashutosh Banerjee、Dirk Schepmann、Jens Köhler、Ernst-Ulrich Würthwein、Bernhard Wünsch

  DOI：10.1016/j.bmc.2010.09.047

  日期：2010.11.15

  A series of chiral non-racemic dexoxadrol analogues with various substituents in position 4 of the piperidine ring was synthesized and pharmacologically evaluated. Only the enantiomers having (S)-configuration at the 2-position of the piperidine ring and 4-position of the dioxolane ring were considered. Key steps in the synthesis were an imino-Diels-Alder reaction of enantiomerically pure imine (S)-13, which had been obtained from D-mannitol, with Danishefsky's Diene 14 and the replacement of the p-methoxybenzyl protective group with a Cbz-group. It was shown that (S,S)-configuration of the ring junction (position 2 of the piperidine ring and position 4 of the dioxolane ring) and axial orientation of the C-4-substituent ((4S)-configuration) are crucial for high NMDA receptor affinity. 2-(2,2-Diphenyl-1,3-dioxolan-4-yl)piperidines with a hydroxy moiety ((S,S,S)-5, K-i = 28 nM), a fluorine atom ((S,S,S)-6, WMS-2539, K-i = 7 nM) and two fluorine atoms ((S,S)-7, K-i = 48 nM) in position 4 represent the most potent NMDA antagonists with high selectivity against sigma(1) and sigma(2) receptors and the polyamine binding site of the NMDA receptor. The NMDA receptor affinities of the new ligands were correlated with their electrostatic potentials, calculated gas phase proton affinities (negative enthalpies of deprotonation) and dipole moments. According to these calculations decreasing proton affinity and increasing dipole moment are correlated with decreasing NMDA receptor affinity. (C) 2010 Elsevier Ltd. All rights reserved.