(2R,3R)-2,3-O-Isopropylidenepentadecan-1-ol | 161615-37-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R)-2,3-O-Isopropylidenepentadecan-1-ol
• 英文别名: (4R,5R)-5-dodecyl-4-hydroxymethyl-2,2-dimethyl-1,3-dioxolane；[(4R,5R)-5-dodecyl-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
• CAS: 161615-37-8
• 化学式: C₁₈H₃₆O₃
• 分子量: 300.482
• InChiKey: AEYAIECMFRJTEO-IAGOWNOFSA-N

物化性质

• 沸点：
  384.0±17.0 °C(Predicted)
• 密度：
  0.909±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  21
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R)-2,3-O-Isopropylidenepentadecan-1-ol 在 咪唑 、 六甲基磷酰三胺 、 N-氯代丁二酰亚胺 、 正丁基锂 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 (R)-tert-butyldimethyl(pentadec-1-yn-3-yloxy)silane
  参考文献：
  名称：

  首次不对称合成含6-羟基-4-鞘氨醇的神经酰胺。使用手性炔丙醇制备人皮肤中发现的脂质。

  摘要：

  最近在人的皮肤中发现了含6-羟基-（4E）-鞘氨醇的神经酰胺。我们在这里介绍了6S和6R非对映异构体2和3的首次合成，它们代表具有两个烯丙基羟基的（2S，3R）-神经酰胺（1）的类似物。分别通过α，β-不饱和酯13和烯丙基氯化物22的不对称二羟基化制备的手性炔丙醇8和11分别用作2和3的前体。 1-丝氨酸衍生的醛26分别提供恶唑烷中间体27和33.酸介导的恶唑烷脱保护，然后N-酰化和桦木还原，完成2和3的合成。

  DOI：

  10.1021/jo026240+
• 作为产物：
  描述：

  (-)-2,3-O-亚异丙基-D-苏力糖醇 在 palladium on activated charcoal 正丁基锂 、 草酰氯 、 氨 、 氢气 、 lithium 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.5h， 生成 (2R,3R)-2,3-O-Isopropylidenepentadecan-1-ol
  参考文献：
  名称：

  Synthetic Studies toward Mono-THF Annonaceous Acetogenins: A Diastereoselective and Convergent Approach to Corossolone and (10RS)-Corossoline

  摘要：

  This paper describes a diastereoselective approach to the total syntheses of both corossolone (1) and (10RS)-corossoline (2), two naturally occurring cytotoxic annonaceous acetogenins from Annona muricata. 2,3-O-Isopropylidene-D-threitol (3) has be en used as the chiral pool for the preparation of (5R,6R)-5-hydroxy-6-[(tert-butyldimethylsilyl)oxy]-1-octadecene (10). Epoxidation of 10 with m-CPBA and intramolecular ring closure in one pot gave a trans-THF intermediate 11 as the major product. The subsequent reagent-controlled asymmetric propargylation was achieved by treatment of the aldehyde derived from 11 with 2-allenyl-1,3,2-dioxaborolane-(4S,5S)-dicarboxylic acid bis-(1'-methylethyl) ester to afford compound 12 with the threo-trans-threo THF moiety with excellent diastereoselectivity. Epoxide 21 prepared from ethyl L-lactate and undecenoic acid according to our previous methodology was treated with alkynyl anion 13 derived from 12 in the presence of BF3-OEt(2) to give the regioselective ring-opening product 22 with the whole skeleton of the target molecule. Finally, beta-elimination followed by deprotection or by oxidation and then deprotection afforded corossolone and (10RS)-corossoline, whose physical data are coincident with those of the natural products.

  DOI：

  10.1021/jo00110a019

文献信息

• Preparation of chiral propargylic alcohols from α,β-unsaturated esters
  作者：Jiong Chun、Hoe-Sup Byun、Robert Bittman

  DOI：10.1016/s0040-4039(02)01968-8

  日期：2002.11

  A series of chiral propargylic alcohols with high enantiomeric excess was prepared by asymmetric dihydroxylation of alpha,beta-unsaturated esters, conversion of the diols to 4-(chloromethyl)-1,3-dioxolane intermediates, and base-induced elimination. (C) 2002 Elsevier Science Ltd. All rights reserved.
• First Asymmetric Synthesis of 6-Hydroxy-4-Sphingenine-Containing Ceramides. Use of Chiral Propargylic Alcohols To Prepare a Lipid Found in Human Skin
  作者：Jiong Chun、Hoe-Sup Byun、Robert Bittman

  DOI：10.1021/jo026240+

  日期：2003.1.1

  present here the first synthesis of the 6S and 6R diastereoisomers 2 and 3, which represent analogues of (2S,3R)-ceramide (1) having two allylic hydroxyl groups. Chiral propargylic alcohols 8 and 11, which were prepared by asymmetric dihydroxylation of alpha,beta-unsaturated ester 13 and allylic chloride 22, respectively, were employed as precursors of 2 and 3. Nucleophilic addition of lithiated TBS-protected

  最近在人的皮肤中发现了含6-羟基-（4E）-鞘氨醇的神经酰胺。我们在这里介绍了6S和6R非对映异构体2和3的首次合成，它们代表具有两个烯丙基羟基的（2S，3R）-神经酰胺（1）的类似物。分别通过α，β-不饱和酯13和烯丙基氯化物22的不对称二羟基化制备的手性炔丙醇8和11分别用作2和3的前体。 1-丝氨酸衍生的醛26分别提供恶唑烷中间体27和33.酸介导的恶唑烷脱保护，然后N-酰化和桦木还原，完成2和3的合成。
• Synthetic Studies toward Mono-THF Annonaceous Acetogenins: A Diastereoselective and Convergent Approach to Corossolone and (10RS)-Corossoline
  作者：Zhu-Jun Yao、Yu-Lin Wu

  DOI：10.1021/jo00110a019

  日期：1995.3

  This paper describes a diastereoselective approach to the total syntheses of both corossolone (1) and (10RS)-corossoline (2), two naturally occurring cytotoxic annonaceous acetogenins from Annona muricata. 2,3-O-Isopropylidene-D-threitol (3) has be en used as the chiral pool for the preparation of (5R,6R)-5-hydroxy-6-[(tert-butyldimethylsilyl)oxy]-1-octadecene (10). Epoxidation of 10 with m-CPBA and intramolecular ring closure in one pot gave a trans-THF intermediate 11 as the major product. The subsequent reagent-controlled asymmetric propargylation was achieved by treatment of the aldehyde derived from 11 with 2-allenyl-1,3,2-dioxaborolane-(4S,5S)-dicarboxylic acid bis-(1'-methylethyl) ester to afford compound 12 with the threo-trans-threo THF moiety with excellent diastereoselectivity. Epoxide 21 prepared from ethyl L-lactate and undecenoic acid according to our previous methodology was treated with alkynyl anion 13 derived from 12 in the presence of BF3-OEt(2) to give the regioselective ring-opening product 22 with the whole skeleton of the target molecule. Finally, beta-elimination followed by deprotection or by oxidation and then deprotection afforded corossolone and (10RS)-corossoline, whose physical data are coincident with those of the natural products.