(3-Hydroxy-3-methylbutyl)triphenylphosphoniumbromid | 67883-18-5

• 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: (3-Hydroxy-3-methylbutyl)triphenylphosphoniumbromid
• 英文别名: (3-Hydroxy-3-methylbutyl)-triphenylphosphonium；(3-Hydroxy-3-methylbutyl)-triphenylphosphanium;bromide
• CAS: 67883-18-5
• 化学式: Br*C₂₃H₂₆OP
• 分子量: 429.337
• InChiKey: ZTTBFZRGZHSYIH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.15
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3-Hydroxy-3-methylbutyl)triphenylphosphoniumbromid 在 platinum(IV) oxide 重铬酸吡啶 、 四丁基氟化铵 、 甲基锂 、 氢气 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 艾地骨化醇中间体
  参考文献：
  名称：

  有效合成25-羟基Windaus-Grundmann酮

  摘要：

  本文描述了从Inhoffen-Lythgoe二醇中短而有效地合成25-羟基Windaus-Grundmann酮的方法（七个步骤，总计70％）。合成中最相关的特征是由便宜的和可商购的起始原料制备维蒂希试剂3。可以以毫克数的量获得纯3，以实现清洁有效的维蒂希反应。

  DOI：

  10.1016/s0040-4039(00)01224-7
• 作为产物：
  描述：

  4-溴-2-甲基-2-丁醇 、 三苯基膦 以 乙腈 为溶剂， 反应 24.0h， 以100%的产率得到(3-Hydroxy-3-methylbutyl)triphenylphosphoniumbromid
  参考文献：
  名称：

  有效合成25-羟基Windaus-Grundmann酮

  摘要：

  本文描述了从Inhoffen-Lythgoe二醇中短而有效地合成25-羟基Windaus-Grundmann酮的方法（七个步骤，总计70％）。合成中最相关的特征是由便宜的和可商购的起始原料制备维蒂希试剂3。可以以毫克数的量获得纯3，以实现清洁有效的维蒂希反应。

  DOI：

  10.1016/s0040-4039(00)01224-7

文献信息

• Neue Synthesen von 1α,25-Dihydroxycholesterin
  作者：Andor Färst、Ludvik Labler、Werner Meier

  DOI：10.1002/hlca.19820650524

  日期：1982.7.28

  New Syntheses of 1α,25-Dihydroxycholesterol

  1α，25-二羟基胆固醇的新合成
• Synthesis and Conformational Analysis of 17α,21-Cyclo-22-Unsaturated Analogues of Calcitriol
  作者：Ricardo Riveiros、Antonio Rumbo、Luis A. Sarandeses、Antonio Mouriño

  DOI：10.1021/jo0625195

  日期：2007.7.1

  Six new calcitriol analogues, conformationally restricted at their side chain by the introduction of both a cyclopropane ring at C17−C20 and a double or triple bond at C22, were synthesized using the Wittig−Horner approach to construct the triene system. The six CD-ring and side-chain bearing fragments were prepared from ketone 14 by a divergent route to generate both series of epimers at C20, followed

  六种新的骨化三醇类似物，通过在Wi-Fi-Horner方法中在C17-C20处引入环丙烷环和在C22处引入双键或三键，在其侧链上受到构象限制，从而合成了三烯系统。通过发散路线从酮14制备六个带有CD环和侧链的片段，以在C20产生两个系列差向异构体，然后进行立体选择性环丙烷化。（E）-烯基侧链通过维蒂希反应合成。炔基侧链通过Corey-Fuchs同源制备，然后进行烷基化。（Z）-烯基侧链通过部分氢化由先前的炔烃制备。20- Epi与具有C20天然立体化学的相应类似物相比，该类似物与VDR的结合更牢固。这些结果可以通过构象分析和与VDR配体结合域的疏水相互作用来推论。
• Photoinduced Alcoholic α‐C−H Bond Anti‐Markovnikov Addition to Vinylphosphonium Bromides Followed by Wittig Olefination: Two‐Step Protocol for α‐C−H Allylic Alkylation of Alcohols
  作者：Masaki Yoshida、Masaya Sawamura、Yusuke Masuda

  DOI：10.1002/cctc.202200744

  日期：2022.9.20

  Photocatalytic Synthesis: A two-step protocol for the α-allylic alkylation of alcohols consisting of photocatalytic anti-Markovnikov addition of the α-C−H bond of alcohols to vinylphosphonium bromides and subsequent Wittig olefination with aldehydes is reported. The protocol is marked by simplicity of the photoreaction system with a single catalyst and broad scope of alcohols, ranging from readily

  光催化合成：报告了醇的 α-烯丙基烷基化的两步方案，该方案由醇的 α-C-H 键光催化反马尔科夫尼科夫加成到乙烯基溴化鏻和随后与醛的 Wittig 烯化组成。该协议的特点是光反应系统的简单性，具有单一催化剂和广泛的醇类，从现成的化学原料到功能化分子。
• Development of Analogues of 1α,25‐Dihydroxyvitamin D ₃ with Biased Side‐Chain Orientation: C20 Methylated Des‐C,D‐homo Analogues
  作者：Freek Vrielynck、Dirk Van Haver、Maurits Vandewalle、Lieve Verlinden、Annemieke Verstuyf、Roger Bouillon、Gianluca Croce、Pierre De Clercq

  DOI：10.1002/ejoc.200801183

  日期：2009.4

  AbstractThe discovery that 1α,25‐dihydroxyvitamin D3 is effective in the inhibition of cellular proliferation and in the induction of cellular differentiation has led to a search for analogues in which these activities and the classical calcemic activity of the hormone are dissociated. In this context, the synthesis and biological evaluation are reported for six CD‐ring modified structural analogues that were conceived so as to enforce a particular orientation of the 25‐hydroxylated side chain. The analogues are characterized by the absence of the C‐ring and the presence of an unnatural six‐membered D‐ring. The biased side‐chain orientations are realized through the stereocontrolled incorporation of methyl substituents at positions C13/C20 and C16/C20. Comparison of the results of the biological evaluation and conformational analysis of the side chain confirms the existence of a relationship between inhibition of MCF‐7 breast cancer cell proliferation and side chain geometry.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• 26-Desmethyl-2-methylene-22-ene-19-nor-1α,25-dihydroxyvitamin D3 compounds selectively active on intestine
  作者：Grazia Chiellini、Pawel Grzywacz、Lori A. Plum、Margaret Clagett-Dame、Hector F. DeLuca

  DOI：10.1016/j.steroids.2014.01.012

  日期：2014.5

  Six new analogs of 2-methylene-19-nor-1 alpha,25-dihydroxyvitamin D-3, 6-7 and 8a,b-9a,b, have been synthesized. All compounds are characterized by a trans double bond located in the side chain between C-22 and C-23. While compounds 6 and 7 possess C-26 and C-27 methyls, compounds 8a,b and 9a,b lack one of these groups. A Lythgoe-based synthesis, employing the Wittig-Horner reaction was used for these preparations. Two different types of Delta E-22-25-hydroxy Grundmann's ketone, having either only one stereogenic center located at position C-20 (20 and 21), or two stereogenic centers located at 20- and 25-positions (24a,b-25a,b) were obtained by a multi-step procedure from commercial vitamin D-2. The introduction of a double bond at C-22 appeared to lower biological activity in vitro and in vivo. Further removal of a 26-methyl in these analogs had little effect on receptor binding, HL-60 differentiation and CYP24A expression but markedly diminished or eliminated in vivo activity on bone calcium mobilization while retaining activity on intestinal calcium transport. (C) 2014 Elsevier Inc. All rights reserved.