(4R,5R)-2-Allyl-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazasilolidine | 596851-24-0

• 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: (4R,5R)-2-Allyl-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazasilolidine
• 英文别名: (4R,5R)-2-chloro-3,4-dimethyl-5-phenyl-2-prop-2-enyl-1,3,2-oxazasilolidine
• CAS: 596851-24-0
• 化学式: C₁₃H₁₈ClNOSi
• 分子量: 267.831
• InChiKey: XHCRAANIMMYPDV-HWURVSIFSA-N

物化性质

• 沸点：
  299.7±50.0 °C(Predicted)
• 密度：
  1.086 g/mL at 25 °C

计算性质

• 辛醇/水分配系数(LogP)：
  3.44
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4R,5R)-2-Allyl-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazasilolidine 、 间三氟甲基苯乙烯 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 氯仿 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  Asymmetric Allylation, Crotylation, and Cinnamylation of N-Heteroaryl Hydrazones

  摘要：

  A new class of N-heteroaryl hydrazones has been developed as an alternative to N-acylhydrazones and 2-aminophenol-derived imines in asymmetric allylation, crotylation, and cinnamylation reactions with chiral allylchlorosilanes. The hydrazones are readily and inexpensively prepared, perform well in the allylation chemistry, and more importantly, the product hydrazides may be smoothly reduced by Pd(OH)(2)-catalyzed hydrogenation to reveal the corresponding amine products.

  DOI：

  10.1021/ol9026864

文献信息

• A Macrocyclic Approach to Tetracycline Natural Products. Investigation of Transannular Alkylations and Michael Additions
  作者：Joseph S. Wzorek、Thomas F. Knöpfel、Ioannis Sapountzis、David A. Evans

  DOI：10.1021/ol302691j

  日期：2012.12.7

  presented. The pivotal intermediate is identified as macrocycle III. The two interior bonds (C4a–C12a and C5a–C11a) are to be constructed through sequential transannular Michael additions (III–II) and compression-promoted transannular isoxazole alkylations from intermediate II.

  提出了一种新的四环素核心结构方法。关键中间体被确定为大环III。两个内部键（C4a–C12a和C5a–C11a）将通过顺序的跨环Michael加成（III – II）和由中间体II压缩促进的跨环异恶唑烷基化来构建。
• A thiocyanopalladation/carbocyclization transformation identified through enzymatic screening: stereocontrolled tandem C–SCN and C–C bond formation
  作者：G. Malik、R. A. Swyka、V. K. Tiwari、X. Fei、G. A. Applegate、D. B. Berkowitz

  DOI：10.1039/c7sc04083k

  日期：——

  this new transformation with asymmetric allylation and Grubbs ring-closing metathesis provides for a streamlined enantio- and diastereoselective entry into the oxabicyclo[3.2.1]octyl core of the natural products massarilactone and annuionone A, as also evidenced by low temperature X-ray crystal structure determination. Utilizing this bicyclic scaffold, we demonstrate the versatility of the thiocyanate

  在这里，我们描述了一种正式的硫氰基缩合/碳环化转化及其参数化和优化方法，该方法使用了新的基于高温板的可视比色酶促筛选方法进行反应发现。碳环化步骤导致C–SCN键与C–C键结构串联形成，并且具有很高的立体选择性，对带有烯丙基取代基的底物显示几乎绝对的1,2-抗立体诱导（5个例子），并且几乎绝对的1,3-同步-立体诱导（16个例子）用于带有炔丙基取代的底物。基于这些高水平的立体感应，1,2-立体感应对环化底物几何形状的依赖性以及通常高度偏爱反式乙烯基硫氰酸酯烯的几何形状，提出了一种机械模型，其中涉及（i）Pd（II）-烯炔配位；（ii）氰基氰基甲酸酯化；（iii）迁移插入和（iv）β-消除。缺乏在未活化的底物上平稳进行并允许保留SCN部分的过渡金属介导的C-SCN键形成的例子。然而，硫氰酸盐官能团对于生物物理化学（振动斯塔克效应）和药物化学（S，N-杂环结构）具有重要价值。标题转换可容纳C，O
• Studies toward the Unique Pederin Family Member Psymberin: Full Structure Elucidation, Two Alternative Total Syntheses, and Analogs
  作者：Yu Feng、Xin Jiang、Jef K. De Brabander

  DOI：10.1021/ja3057612

  日期：2012.10.17

  Two synthetic approaches to psymberin have been accomplished. A highly convergent first generation synthesis led to the complete stereochemical assignment and demonstrated that psymberin and irciniastatin A are identical compounds. This synthesis featured a diastereoselective aldol coupling between the aryl fragment and a central tetrahydropyran core and a novel one-pot procedure to convert an amide, via intermediacy of a sensitive methyl imidate, to the N-acyl aminal reminiscent of psymberin. The highlights of the second generation synthesis include an efficient iridium-catalyzed enantioselective bisallylation of neopentyl glycol and a stepwise Sonogashira coupling/cycloisomerization/reduction sequence to construct the dihydroisocoumarin unit. The two synthetic avenues were achieved in 17-18 steps (longest linear sequence, similar to 14-15 isolations) from 3 fragments prepared in 7-8 (first generation) and 3-8 (second generation) steps each. This convergent approach allowed for the preparation of sufficient amounts of psymberin (similar to 0.5 g) for follow-up biological studies. Meanwhile, our highly flexible strategy enabled the design and synthesis of multiple analogs, including a psymberin pederin hybrid, termed psympederin, that proved crucial to a comprehensive understanding of the chemical biology of psymberin and related compounds that will be described in a subsequent manuscript.
• WO2008/153801
  申请人：——

  公开号：——

  公开（公告）日：——
• Allylsilane–Vinylarene Cross-Metathesis Enables a Powerful Approach to Enantioselective Imine Allylation
  作者：John D. Huber、Nicholas R. Perl、James L. Leighton

  DOI：10.1002/anie.200705621

  日期：2008.4.7