2-bromo-1-ethoxy-2-methyl-1-trimethylsilyoxyethene | 153645-08-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-bromo-1-ethoxy-2-methyl-1-trimethylsilyoxyethene
• 英文别名: 2-bromo-1-ethoxy-2-methyl-1-trimethylsiloxyethene；2-bromo-1-ethoxy-1-trimethylsiloxypropene；[(2-Bromo-1-ethoxyprop-1-en-1-yl)oxy](trimethyl)silane；(2-bromo-1-ethoxyprop-1-enoxy)-trimethylsilane
• CAS: 153645-08-0
• 化学式: C₈H₁₇BrO₂Si
• 分子量: 253.211
• InChiKey: YOVRJFCRDLGZLZ-UHFFFAOYSA-N

物化性质

• 沸点：
  196.5±35.0 °C(predicted)
• 密度：
  1.175±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.46
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-bromo-1-ethoxy-2-methyl-1-trimethylsilyoxyethene 在 三乙基硼 2,6-二甲基吡啶 、 硼烷四氢呋喃络合物 、 1,3,2-oxazaborolidin-5-one 、 三正丁基氢锡 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 15.0h， 生成 (2R,3S)-3-hydroxy-2-methyl-3-phenyl-propionic acid ethyl ester
  参考文献：
  名称：

  基于手性 1,3,2-Oxazaborolidin-5-one 促进的不对称醛醇反应和非对映选择性自由基还原的本质上对映纯素和反丙酸酯醛醇加合物的不同合成

  摘要：

  本质上，对映纯的合成和反丙醇醛加合物是使用一种新的策略不同地合成的，该策略利用高度对映选择性的 1,3,2-oxazaborolidin-5-one-促进的醛醇反应与衍生自乙基 2-溴的乙烯酮甲硅烷基缩醛丙酸盐和高度非对映选择性的自由基脱溴反应。这些程序提供的产率增加到可用于实际合成的水平。

  DOI：

  10.1246/bcsj.74.1485
• 作为产物：
  描述：

  三甲基氯硅烷 、 2-溴丙酸乙酯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 2-bromo-1-ethoxy-2-methyl-1-trimethylsilyoxyethene
  参考文献：
  名称：

  Stereoselective Hydrogen Transfer Reactions Involving Acyclic Radicals. Tandem Substituted Tetrahydrofuran Formation and Stereoselective Reduction: Synthesis of the C17-C22 Subunit of Ionomycin

  摘要：

  The tandem iodoetherification reaction and stereoselective reduction of acyclic radicals has been used in the stereocontrolled synthesis of substituted tetrahydrofurans. Such a tetrahydrofuran intermediate is regioselectively cleaved using Me(2)BBr to reveal the acyclic array 2 which represents the C-17-C-22 subunit of ionomycin. In experiments that provide for a better understanding of hydrogen transfer reactions involving acyclic radicals, a significant improvement in the stereoselectivity is observed when the two substituents at the stereogenic center alpha to the radical are imbedded in a cycle (''cycle effect''). A mechanistic rationale is discussed.

  DOI：

  10.1021/jo00084a040

文献信息

• Regulated-Stereoselective Construction of Thirteen Stereogenic Centers Necessary for the Frame of (+)-Discodermolide, Based on Iterative Lewis Acid-Promoted Aldol Reactions
  作者：Syun-ichi Kiyooka、Kazi Abdus Shahid、Fumitaka Goto、Momotoshi Okazaki、Yoshihiro Shuto

  DOI：10.1021/jo034901c

  日期：2003.10.1

  and diastereoselective (BF(3).OEt(2) and TiCl(4)) aldol reactions with the silylketene acetal, coupled with diastereoselective radical debrominations (Bu(3)SnH, Et(3)B, with or without MgBr(2)), were used iteratively. This aldol reaction strategy for the construction of the polypropionate frame dramatically shortened the steps needed for the construction of the final segments.

  包含（+）-discodermolide框架所需的13个立体异构中心的C（1）-C（13）和C（15）-C（21）片段是由一种常见的外消旋体以良好至优异的对映选择性和非对映选择性合成的醛，衍生自2-甲基-1,3-丙二醇。外消旋醛与2-溴丙酸乙酯衍生的甲硅烷基乙烯酮缩醛的对映体选择性醛醇缩合反应，在手性草氮杂硼烷酮存在下，用N-甲苯磺酰基-（R）-和-（S）-缬氨酸和BH（3）原位制备THF，在动力学控制下进行，得到具有高度对映选择性的立体三单元组。对映选择性（手性硼烷）和非对映选择性（BF（3）.OEt（2）和TiCl（4））与硅烷基乙烯酮缩醛的醛醇缩合反应，与非对映选择性自由基脱溴反应（Bu（3）SnH，Et（3）B，或没有MgBr（2）），被迭代使用。这种用于聚丙烯酸酯框架构建的羟醛反应策略大大缩短了构建最终链段所需的步骤。
• A short synthesis of the C15–C21 segment of (+)-discodermolide, based on an asymmetric approach from achiral 2-methyl-1,3-propanediol to versatile enantiopure stereotriads
  作者：Kazi A. Shahid、Yong-Nan Li、Momotoshi Okazaki、Yoshihiro Shuto、Fumitaka Goto、Syun-ichi Kiyooka

  DOI：10.1016/s0040-4039(02)01373-4

  日期：2002.9

  A new approach was developed to versatile enantiopure stereotriads using chiral oxazaborolidinone-promoted asymmetric aldol reaction of a racemic aldehyde with a bromo silyl nucleophile. A short synthesis of the C15–C21 segment of (+)-discodermolide was achieved by elongation of one of the stereotriads with further diastereoselective aldol reaction with the same nucleophile.

  已开发出一种新的方法，用于使用手性草酰氮杂硼硼烷酮促进的外消旋醛与溴甲硅烷基亲核试剂的不对称醛醇缩合反应形成的多功能对映体纯立体三联体。（+）-discodermolide的C 15 –C 21片段的短合成是通过延长一个立体三单元组与同一亲核试剂进一步进行非对映选择性醛醇缩合反应而实现的。
• A practical synthesis of essentially enantiopure syn-propionate aldols using a chiral oxazaborolidinone-promoted asymmetric aldol reaction coupled with radical reduction
  作者：Syun-ichi Kiyooka、Kazi A. Shahid、Mostofa A. Hena

  DOI：10.1016/s0040-4039(99)01278-2

  日期：1999.8

  Essentially enantiopure syn-propionate aldols (>98% ee) were prepared by a chiral oxazaborolidinone-promoted asymmetric aldol reaction, followed by a diastereoselective radical reduction with Bu3SnH and Et3B, which was carried out under chelation control. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Efficient enantio- and diastereoselective synthesis of enantiopure syn-α-bromo-β-hydroxy-α-methylpropionate esters and their cis-α,β-epoxy derivatives based on a chiral oxazaborolidinone-promoted asymmetric aldol reaction
  作者：Syun-ichi Kiyooka、Kazi A Shahid

  DOI：10.1016/s0957-4166(00)00089-6

  日期：2000.4

  syn-alpha-Bromo-beta-hydroxy-alpha-methylpropionate esters were prepared in high diastereoselectivity with essentially enantiopure state by employing the chiral oxazaborolidinone-promoted asymmetric aldol reaction with beta-bromo-beta-methylketene silyl acetal. The subsequent subjection of the alpha-bromo-beta-hydroxy esters to basic conditions led to the quantitative transformation to the corresponding enantiopure cis-alpha,beta-epoxy derivatives, (C) 2000 Elsevier Science Ltd. All rights reserved.
• A straightforward, highly stereoselective construction of eight stereogenic centers in (+)-discodermolide C1–C13 segment, based on a strategy of iterative aldol reactions
  作者：Kazi A. Shahid、Jahan Mursheda、Momotoshi Okazaki、Yoshihiro Shuto、Fumitaka Goto、Syun-ichi Kiyooka

  DOI：10.1016/s0040-4039(02)01389-8

  日期：2002.9

  The eight stereogenic centers were introduced into the C-1-C-13 segment of (+)-discodermolide by iterative aldol reactions with quite a high level of selection. (C) 2002 Elsevier Science Ltd. All rights reserved.