tert-butyl-[(1S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-[(2R)-oxiran-2-yl]ethoxy]-dimethylsilane | 1106401-93-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl-[(1S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-[(2R)-oxiran-2-yl]ethoxy]-dimethylsilane
• CAS: 1106401-93-7
• 化学式: C₁₅H₃₀O₄Si
• 分子量: 302.486
• InChiKey: SDTAPLNDACVPCZ-FRRDWIJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.32
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl-[(1S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-[(2R)-oxiran-2-yl]ethoxy]-dimethylsilane 在 咪唑 、 silica-supported sodium periodate 、 水 、 三乙基硼氢化锂 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.33h， 生成 (3S,4S,6S)-4-(tert-butyldimethylsilyloxy)-6-(triisopropylsilyloxy)hept-1-en-3-ol
  参考文献：
  名称：

  Synthesis of hept-6-en-2,4,5-triols and hept-6-en-2,3,5-triols

  摘要：

  In a systematic effort to establish the relative as well as absolute configurations of two natural products isolated from Asomycete Daldinia concentrica, four independent (non-antipodal) diastereomers of hept-6-en-2,4,5-triol, the structure previously proposed for the natural products, were synthesized in enantiopure forms through a chiral-pool route and their optical rotation as well as NMR data were recorded. Although these four synthetic isomers cover all possible relative configurations the originally assigned triol may have, none of them gave spectroscopic data compatible with those reported for the natural products. Similar negative results were also obtained with a group of four non-antipodal diastereomers of hept-6-en-2,3,5-triol. The genuine structures of the natural products are therefore to be re-assigned. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.01.091
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 (2R,3S,5RS)-5,6-Epoxy-1,2-O-isopropylidenehexane-1,2,3-triol 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以91%的产率得到tert-butyl-[(1S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-[(2R)-oxiran-2-yl]ethoxy]-dimethylsilane
  参考文献：
  名称：

  Synthesis of hept-6-en-2,4,5-triols and hept-6-en-2,3,5-triols

  摘要：

  In a systematic effort to establish the relative as well as absolute configurations of two natural products isolated from Asomycete Daldinia concentrica, four independent (non-antipodal) diastereomers of hept-6-en-2,4,5-triol, the structure previously proposed for the natural products, were synthesized in enantiopure forms through a chiral-pool route and their optical rotation as well as NMR data were recorded. Although these four synthetic isomers cover all possible relative configurations the originally assigned triol may have, none of them gave spectroscopic data compatible with those reported for the natural products. Similar negative results were also obtained with a group of four non-antipodal diastereomers of hept-6-en-2,3,5-triol. The genuine structures of the natural products are therefore to be re-assigned. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.01.091

文献信息

• Synthesis and configuration of the nonadecenetriol isolated from seeds of Persea americana
  作者：Xin Yan、Shao-Min Zhang、Yikang Wu、Po Gao

  DOI：10.1039/c1ob05898c

  日期：——

  In an effort to establish the relative as well as absolute configuration of the trypanocidally active natural nonadec-6-en-1,2,4-triol isolated from Persea americana, the (2S,4R), (2S,4S), and (2R,4R) isomers were synthesized. The stereogenic centers taken from enantiopure chiral epoxy building blocks derived from inexpensive and readily available D-glucolactone. The (2R,4R) isomer gave 1H and 13C NMR as well as specific rotation in excellent consistence with those reported for the natural triol.

  为了确定从鳄梨中分离出的具有杀锥虫活性的天然十九碳-6-烯-1,2,4-三醇的相对和绝对构型，合成了(2S,4R)、(2S,4S)和(2R,4R)三种异构体。这些手性中心来自于由廉价且易得的D-古洛内酯衍生的对映纯手性环氧构建模块。其中，(2R,4R)异构体在氢谱和碳谱核磁共振以及比旋光度方面与报道的天然三醇数据高度一致。
• An Enantioselective Convergent Route to Pamamycin 621A
  作者：Guo-Bao Ren、Yi-Xian Huang、Ya-Ping Sun、Zhong-Han Li、Yikang Wu

  DOI：10.1021/jo100774n

  日期：2010.8.6

  approach to the total synthesis of natural antibiotic pamamycin 621A is described, in which the stereogenic centers at the C-13 and C-15 were taken from a chiral building block derived from the inexpensive d-glucolactone while all others (except the C-10) were installed via chiral auxiliary-induced asymmetric Evans/Crimmins aldol reactions. In the synthesis of the smaller/lower fragment, an antiselective

  描述了一种完全合成天然抗生素帕马霉素621A的有效方法，其中C-13和C-15的立体异构中心取自廉价d的手性结构单元。-葡糖内酯，而其他所有（C-10除外）则通过手性辅助诱导的不对称Evans / Crimmins aldol反应进行安装。在较小/较低片段的合成中，仅当存在化学计算量（而不是文献中报道的催化量）的氯化镁时，才发生抗选择性埃文斯羟醛缩合反应。在手性助剂存在下，还观察到了吡啶碱基的空间体积对THF环形成的立体化学结果的先前未知的影响。类似地，通过分子内的O-烷基化从带有手性助剂的线性前体以高水平的立体选择性类似地合成了较大/上部片段中的THF环，最显着的是即使在酸性条件下。
• Synthesis and configurations of YF-0200R A and B
  作者：Xiao-Dan Wang、Ze-Jun Xu、Shijun Zhu、Yikang Wu、Yan-Jun Hou

  DOI：10.1016/j.tet.2016.04.033

  日期：2016.6

  samples were in excellent consistency with those reported for the corresponding natural ones. The optical rotations were also compatible with those for the natural ones. The absolute configurations for natural YF-0200R A and B thus could be reliably assigned as (8S) and (8S,10S), respectively.

  首次合成了两种具有天冬酰胺蛋白酶抑制活性的天然不饱和脂肪酸。通过分别使用布朗不对称烯丙基化或衍生自d-葡萄糖的手性结构单元来安装立体异构中心。经由HWE反应引入共轭二烯单元。通过C 6 D 6中的1 H NMR，C C双键的几何结构清楚地显示为（E）。。合成样品的光谱数据与相应天然样品的光谱数据具有极好的一致性。旋光度也与自然旋光度兼容。因此，可以将自然YF-0200RA和B的绝对配置分别可靠地指定为（8 S）和（8 S，10 S）。
• An Aldol Approach to the Total Synthesis of Pamamycin 621 A
  作者：Guo-Bao Ren、Yikang Wu

  DOI：10.1021/ol902290v

  日期：2009.12.17

  Pamamycin 621 A was synthesized through a convergent route, with the THF rings constructed from Evans aldols in the presence of the chiral auxiliaries without suffering racemization or elimination. The basic amino group was introduced at a late stage through reduction of an azido group with n-Bu3SnH, which also demonstrates for the first time the great potential of this largely forgotten reduction protocol in synthesis of multifunctional substrates.
• Facile access to some chiral building blocks. Synthesis of verbalactone and exophilin A
  作者：Jian-Zhong Wu、Jian Gao、Guo-Bao Ren、Zhi-Bin Zhen、Yihua Zhang、Yikang Wu

  DOI：10.1016/j.tet.2008.10.050

  日期：2009.1

  D-Glucono-1,5-lactone, all inexpensive carbohydrate, was elaborated into chiral building blocks readily applicable in synthesis via practical routes without involving any expensive reagents or tedious operations. Application Of Such chiral building blocks in total synthesis is then exemplified through construction of verbalactone and exophilin A. The latter compound has not been synthesized to date. (C) 2008 Elsevier Ltd. All rights reserved.