(2S,3S)-2-[(4R,5R)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-yl]hex-5-en-3-ol | 932739-33-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S)-2-[(4R,5R)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-yl]hex-5-en-3-ol
• 英文别名: (4S,5S,6R,7R)-6,7-isopropylidenedioxy-5-methyl-7-phenylhept-1-en-4-ol
• CAS: 932739-33-8
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: UXMNZENFMZSSCC-ARLBYUKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  (2S,3S)-2-[(4R,5R)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-yl]hex-5-en-3-ol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 2,4,6-三氯苯甲酰氯 、 4-甲基苯磺酸吡啶 、 N,N-二异丙基乙胺 、 三氟乙酸 、 原甲酸三甲酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 35.0h， 生成 cryptophycin 24
  参考文献：
  名称：

  Total synthesis of cryptophycin-24 (arenastatin A) via Prins cyclization

  摘要：

  A stereoselective synthesis of fragment A of cryptophycin is achieved utilizing the versatile Prins cyclization. Subsequently, the total synthesis of cryptophycin-24 (arenastatin A) has been accomplished by coupling it with the depsipeptide subunit. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.09.134
• 作为产物：
  描述：

  methyl (R)-2-[(4R,5R)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-yl]propanoate 在 二异丁基氢化铝 、 magnesium bromide 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 16.25h， 生成 (2S,3S)-2-[(4R,5R)-2,2-dimethyl-5-phenyl-1,3-dioxolan-4-yl]hex-5-en-3-ol
  参考文献：
  名称：

  隐藻素A的短而有效的合成。

  摘要：

  [反应：见正文]两种针对隐藻霉素A的短合成方法包括催化不对称二羟基化作为手性的唯一来源，而所有其他立体异构中心均在底物的控制下引入。第一条路线的关键步骤是乙烯基乙烯基Mukaiyama羟醛加成，它引入在δ碳原子上具有确定构型的α，β-不饱和酯部分。同样地，与烯丙基三丁基锡烷非对映选择性地烯丙基化，可以通过复分解反应将其转化为单元A前体。

  DOI：

  10.1021/ol063032l

文献信息

• Efficient Synthesis of Cryptophycin-52 and Novel<i>para</i>-Alkoxymethyl Unit A Analogues
  作者：Stefan Eißler、Tobias Bogner、Markus Nahrwold、Norbert Sewald

  DOI：10.1002/chem.200901750

  日期：2009.10.26

  respective amino and hydroxy acids. A new synthetic route to unit A allows the selective generation of all four stereogenic centres in a short, efficient and reliable synthesis and contributes to an easier and faster synthesis of cryptophycins. The first two stereogenic centres are introduced by a catalytic asymmetric dihydroxylation, whereas the remaining two stereogenic centres are introduced with

  隐藻素是高度细胞毒性的环状双缩肽的家族。它们显示出对多药耐药肿瘤细胞的抗肿瘤活性。隐藻素由对应于各自的氨基酸和羟基酸的四个构件（AD单元）组成。通往A单元的新合成途径可在短，有效和可靠的合成中选择性生成所有四个立体异构中心，并有助于更轻松，更快速地合成隐藻素。前两个立体异构中心是通过催化不对称二羟基化作用引入的，而其余两个立体异构中心是通过非对映选择性底物控制引入的。立体异构二醇功能还用作环氧化物前体。该方法用于综合本机单元A构建块以及三个制备了隐霉素52和三种类似隐藻霉素的对烷氧基甲基类似物。所述的大环开环-depsipeptides是基于闭环复分解。
• Total synthesis and biological evaluation of fluorinated cryptophycins
  作者：Christine Weiß、Tobias Bogner、Benedikt Sammet、Norbert Sewald

  DOI：10.3762/bjoc.8.231

  日期：——

  Cryptophycins are cytotoxic natural products that exhibit considerable activities even against multi-drug-resistant tumor cell lines. As fluorinated pharmaceuticals have become more and more important during the past decades, fluorine-functionalized cryptophycins were synthesized and evaluated in cell-based cytotoxicity assays. The unit A trifluoromethyl-modified cryptophycin proved to be highly active against KB-3-1 cells and exhibited an IC₅₀ value in the low picomolar range. However, the replacement of the 3-chloro-4-methoxyphenyl-substituent in unit B by a pentafluorophenyl moiety resulted in a significant loss of activity.

  Cryptophycins是细胞毒性天然产物，甚至对多药耐药的肿瘤细胞系表现出相当大的活性。随着氟化制药在过去几十年变得越来越重要，氟功能化的Cryptophycins被合成并在基于细胞的细胞毒性实验中进行了评估。三氟甲基修饰的Cryptophycin A单元被证明对KB-3-1细胞非常活跃，并在低皮克摩尔范围内显示出IC50值。然而，将单元B中的3-氯-4-甲氧基苯基取代为五氟苯基团导致活性显著降低。
• A Novel Asymmetric Synthesis of the Core Octadienoic Acid Unit of Cryptophycins from (R)-2,3-O-Cyclohexylideneglyceraldehyde
  作者：Subrata Chattopadhyay、Dibakar Goswami、Payel Sur、Angshuman Chattopadhyay、Anubha Sharma

  DOI：10.1055/s-0030-1260014

  日期：2011.5

  A facile asymmetric synthesis of the octadienoic acid unit of cryptophycins was developed starting from (R)-2,3-O-cyclohexylideneglyceraldehyde. The key steps of the synthesis are the stereocontrolled generation of the required asymmetric centers through (i) a gallium-mediated highly diastereoselective crotylation of the glyceraldehyde in [bmim][Br], (ii) a stereoselective allylation with allyltributylstannane

  从（R）-2,3- O-环己叉基甘油醛开始开发了一种隐藻霉素的辛二烯酸单元的简便不对称合成方法。合成的关键步骤是通过（i）镓介导的[bmim] [Br]中甘油醛的非对映选择性crotylation立体控制生成所需的不对称中心，（ii）用烯丙基三丁基锡烷进行立体选择性烯丙基化，以及（iii） α-氧化醛中的对映选择性格氏试剂。 不对称合成-手性池-隐藻素-镓-丁酰化-烯丙基化
• Approaches for the Synthesis of Functionalized Cryptophycins
  作者：Benedikt Sammet、Tobias Bogner、Markus Nahrwold、Christine Weiss、Norbert Sewald

  DOI：10.1021/jo101563s

  日期：2010.10.15

  The first syntheses of bioactive cryptophycins functionalized at unit ID were accomplished ina one-pot Staudinger reduction/cyclization step An a/ado precursor for the lower part of the backbone was introduced to minimize protective group chemistry and enable a very convenient synthesis of cryptophycin-52 and unit D eryptophycin analogues containing an ester or a free carboxylic acid for bioconjugations Both new cryptophycin derivatives show high biological activity in cytotoxicity assays
• “Clicktophycin-52”: A Bioactive Cryptophycin-52 Triazole Analogue
  作者：Markus Nahrwold、Tobias Bogner、Stefan Eissler、Spart Verma、Norbert Sewald

  DOI：10.1021/ol1000473

  日期：2010.3.5

  An endocyclic trans-amide linkage within the macrocyclic antitumor agent cryptophycin-52 was replaced by a 1,4-disubstituted 1H-1,2,3-triazole ring. Macrocyclisation of the triazole analogue was accomplished by macrolactamization as well as by Cu(I)-mediated "click"-cyclization. Compared to cryptophycin-52, in vitro cytotoxicity of "clicktophycin-52" against the multidrug resistant human cancer cell line KB-V1 is only slightly reduced.