Triphenyl-(3-trimethylsilanyloxy-propylidene)-λ⁵-phosphane | 110370-82-6

• 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: Triphenyl-(3-trimethylsilanyloxy-propylidene)-λ⁵-phosphane
• 英文别名: triphenyl(3-trimethylsilyloxypropylidene)-λ5-phosphane
• CAS: 110370-82-6
• 化学式: C₂₄H₂₉OPSi
• 分子量: 392.553
• InChiKey: HVOANDVQGGOPBW-UHFFFAOYSA-N

物化性质

• 沸点：
  489.7±47.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  27.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  6-(苄氧基)己醛 、 Triphenyl-(3-trimethylsilanyloxy-propylidene)-λ⁵-phosphane 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  通过区域和立体选择性四氢呋喃环形成策略合成黏液毒素的拟议结构

  摘要：

  描述了提议的粘蛋白（1）结构的对映选择性全合成。粘液毒素是一种从卷花粘膜的生物活性叶片提取物中分离出来的无水产乙酸素，它是第一种含有羟基化三取代四氢呋喃（THF）环的产乙酸素。此天然产物是一种高度有效的和特异性的抗肿瘤抗MCF-7（乳腺癌）细胞系剂（ED 50 = 3.7×10 - 3微克/毫升相比阿霉素，ED 50 = 1.0×10 - 2微克/毫升）。本文所述的总合成具有两个区域选择性和立体选择性的THF成环反应。2,3,5-三取代的THF部分（C13-C17）使用亚甲基间断的环氧二醇的高度区域选择性环化获得，2,5,5-二取代的THF环（C8-C12）可以通过1方便地组装2-正三醇环化策略。合成材料及其两个非对映异构体的光谱数据与天然产物的报道数据不匹配。在对合成分子进行详细的光谱分析的基础上，我们认为光谱差异是由于天然产物的立体化学错配引起的。

  DOI：

  10.1021/jo052073c
• 作为产物：
  描述：

  三甲基氯硅烷 、 (3-羟丙基)三苯基溴化鏻 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.25h， 生成 Triphenyl-(3-trimethylsilanyloxy-propylidene)-λ⁵-phosphane
  参考文献：
  名称：

  通过区域和立体选择性四氢呋喃环形成策略合成黏液毒素的拟议结构

  摘要：

  描述了提议的粘蛋白（1）结构的对映选择性全合成。粘液毒素是一种从卷花粘膜的生物活性叶片提取物中分离出来的无水产乙酸素，它是第一种含有羟基化三取代四氢呋喃（THF）环的产乙酸素。此天然产物是一种高度有效的和特异性的抗肿瘤抗MCF-7（乳腺癌）细胞系剂（ED 50 = 3.7×10 - 3微克/毫升相比阿霉素，ED 50 = 1.0×10 - 2微克/毫升）。本文所述的总合成具有两个区域选择性和立体选择性的THF成环反应。2,3,5-三取代的THF部分（C13-C17）使用亚甲基间断的环氧二醇的高度区域选择性环化获得，2,5,5-二取代的THF环（C8-C12）可以通过1方便地组装2-正三醇环化策略。合成材料及其两个非对映异构体的光谱数据与天然产物的报道数据不匹配。在对合成分子进行详细的光谱分析的基础上，我们认为光谱差异是由于天然产物的立体化学错配引起的。

  DOI：

  10.1021/jo052073c

文献信息

• Total Syntheses of (+)-Australine and (−)-7-Epialexine
  作者：William H. Pearson、Jennifer V. Hines

  DOI：10.1021/jo000689q

  日期：2000.9.1

  naturally occurring 3-(hydroxymethyl)pyrrolizidines. A third approach to these compounds was successful. The transformation of L-xylose into the azido epoxy tosylate 46 was accomplished using two Wittig reactions and an epoxidation, in addition to other standard functional group manipulations. Reductive double-cyclization of 46 afforded the pyrrolizidines 47a and 47b, which were debenzylated to afford

  研究了三种合成3-（羟甲基）吡咯烷核苷的方法，3-类化合物包括多羟基化的吡咯烷啶生物碱alexine（1），australine（2）及其各种立体异构体。在第一种方法中，将叠氮化物分子内环加成到带有末端烷氧基甲基取代基（即21）的富电子的1，3-二烯上，得到脱氢吡咯烷核苷22a和22b，其中22a占优势。提出了这种立体选择性的基本原理。由于将苯基乙烯基硫醚官能团转化成其他有用的官能团遇到困难，因此不可能将主要的非对映异构体22a转化成天然的3-（羟甲基）吡咯烷啶。研究了第二种方法，其中发现叠氮化物与光学纯的St-Bu-取代的二烯（即30）的分子内环加成产生吡咯并核苷31。在这种情况下，烷氧基甲基取代基并入叠氮化物和二烯之间的系链中，而不是二烯本身。二烯30合成中的关键转化是使用烯丙基硼烷R（2）BCH（2）CH = C（TMS）（StBu）将D-阿拉伯糖衍生的叠氮基醛28立体选择性转化为苯
• A Concise Synthesis of (−)-Aplyviolene Facilitated by a Strategic Tertiary Radical Conjugate Addition
  作者：Martin J. Schnermann、Larry E. Overman

  DOI：10.1002/anie.201204977

  日期：2012.9.17

  A second‐generation synthesis of the rearranged spongian diterpene aplyviolene is reported. The key step is the addition of a trialkyl tertiary radical generated by photoredox‐mediated fragmentation of a N‐(acyloxy)phthalimide to an α‐chloropentenone (see scheme). This process fashioned a quaternary stereocenter while combining two units of significant complexity.

  报道了重排海绵二萜 aplyviolene 的第二代合成。关键步骤是将通过光氧化还原介导的N-（酰氧基）邻苯二甲酰亚胺碎裂生成的三烷基叔自由基添加到 α-氯戊烯酮上（参见方案）。这个过程形成了一个四元立体中心，同时结合了两个非常复杂的单元。
• Palladium-catalyzed stereocontrolled cyclization of 1,3-diene monoepoxide: A route to a new synthetic intermediate for de-ab-cholestane derivative.
  作者：Takashi Takahashi、Masahiro Miyazawa、Hiroaki Ueno、Jiro Tsuji

  DOI：10.1016/s0040-4039(00)83905-2

  日期：1986.1

  The optically active (2R, 3R)-3-[(3R)-(E)-Benzyloxymethoxy-5-methyl-1-hexenyl]-2-(3-butenyl)-2-methyl-1-cyclopentanone (8) was synthesized as a precursor of vitamin D3(5) by palladium-catalyzed syn-SN2′ cyclization of [Z,Z(22S, 23R)]-ene oxide 6 as a key reaction.

  旋光的（2R，3R）-3-[（3R）-（E）-苄氧基甲氧基-5-甲基-1-己烯基] -2-（3-丁烯基）-2-甲基-1-环戊酮（8）为通过钯催化的[Z，Z（22S，23R）]-氧化烯6的syn-S N 2'环化反应合成维生素D 3（5）的前体。
• Samarium(II) Iodide-Mediated Reductive Annulations of Ketones Bearing a Distal Vinyl Epoxide Moiety
  作者：Gary A. Molander、Sagar R. Shakya

  DOI：10.1021/jo960335s

  日期：1996.1.1

  Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.
• Synthesis of (-)-slaframine and related indolizidines
  作者：William H. Pearson、Stephen C. Bergmeier、John P. Williams

  DOI：10.1021/jo00040a045

  日期：1992.7

  An enantioselective synthesis of the indolizidine alkaloid (-)-slaframine 1 is reported. Reductive double cyclization of the azido epoxy tosylate 48 afforded the indolizidine 52, which was converted to (-)-slaframine in two steps. The cyclization substrate 48 was prepared in optically pure form from L-glutamic acid. A similar sequence starting with the epoxide 49 allowed the synthesis of (-)-1,8a-diepislaframine 56. Other routes to slaframine were investigated, often using an intramolecular cycloaddition of an azide with an alkene as a key step. Although these routes did not produce slaframine, they illustrated novel and efficient methods for the assembly of the indolizidine skeleton. Cyclization of the azidodiene 20 afforded the indolizidine 21 in one step as a single diastereomer, presumably a result of a chairlike transition state in the initial dipolar cycloaddition. Desulfurization and deprotection produced (-)-8a-epidesacetoxyslaframine 27. Cyclopropylimine rearrangement of 30 gave the indolizidine 31, which was also converted into (-)-8a-epidesacetoxyslaframine 27. Dipolar cycloaddition of 38 gave the 1-pyrroline 39, which was converted to the indolizidine 40 in one operation using Evans' double alkylation of the 1-metalloenamine derivative of 40. Attempted oxidation of 40 to the ketone 41 was unsuccessful, precluding a reductive amination approach to slaframine.