(2S)-2-methyl-3-(triethylsilyl)oxypropanal | 144681-76-5

• 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: (2S)-2-methyl-3-(triethylsilyl)oxypropanal
• 英文别名: (2S)-2-methyl-3-triethylsilyloxypropanal
• CAS: 144681-76-5
• 化学式: C₁₀H₂₂O₂Si
• 分子量: 202.369
• InChiKey: OGCHWLVTRRZEAM-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S)-2-methyl-3-(triethylsilyl)oxypropanal 在 四(三苯基膦)钯 、 正丁基锂 、 偶氮二甲酸二异丙酯 、 4 A molecular sieve 、 diethylzinc 、 四丁基碘化铵 、 N,N-二异丙基乙胺 、 三苯基膦 、 lithium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 65.75h， 生成 Benzoic acid (1S,4S,5S,6S)-1-{(2S,3R)-2-(tert-butyl-dimethyl-silanyloxy)-3-[(2R,4R,5S)-2-(4-methoxy-phenyl)-5-methyl-[1,3]dioxan-4-yl]-butyl}-5-methoxymethoxy-4,6-dimethyl-7-triethylsilanyloxy-hept-2-ynyl ester
  参考文献：
  名称：

  Total Synthesis of (+)-Discodermolide

  摘要：

  The total synthesis of (+)-discodermolide is described. The approach involves assemblage of three key stereotriad subunits through addition of nonracemic allenyltin, -indium, and -zinc reagents to (S)-3-silyloxy-2-methylpropanal derivatives, followed by reduction of the resulting anti,syn- or syn,syn-homopropargylic alcohol adducts to the (E)-homoallylic alcohols and subsequent Sharpless epoxidation. Addition of methyl cuprate reagents of Red-Al to the resultant epoxy alcohols yielded the key precursors, alkyne 4, aldehyde 9, and alcohol 24. Addition of alkyne 4 (as the lithio species 10) to aldehyde 9 afforded the propargylic alcohol 11 as the major stereoisomer. Lindlar hydrogenation and installation of appropriate protecting groups led to aldehyde 17. This was converted to the (Z)-vinylic iodide 18 upon treatment with alpha-iodoethylidene triphenylphosphorane. Suzuki coupling of this vinylic iodide with a boranate derived from iodide 25 led to the coupled product 27 with the complete carbon backbone of (+)-discodermolide and the correct stereochemistry. The synthesis was completed by cleavage of the cyclic PMP acetal at C1 with i-Bu2AlH and three-step oxidation-esterification to the ester 31. Cleavage of the C19 Et3Si ether and C19 carbamate formation followed by cleavage of the remaining alcohol protecting groups, first with DDQ and then aqueous HCl, afforded (+)-discodermolide (36).

  DOI：

  10.1021/jo9811423
• 作为产物：
  描述：

  三乙基氯硅烷 在 咪唑 、 4-二甲氨基吡啶 、 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 (2S)-2-methyl-3-(triethylsilyl)oxypropanal
  参考文献：
  名称：

  Applications of crotyldiisopinocampheylboranes in synthesis: a formal total synthesis of (+)-calyculin A

  摘要：

  报道了海洋代谢产物（+）-卡伊库林A的正式全合成。关键步骤包括（i）使用布朗烯丙基硼化化学来控制同型烯醇阵列的相对和绝对立体化学，从而设置所需的八个立体中心；（ii）在构建天然产物的氰基四烯单元中使用斯蒂尔偶联方法；以及（iii）一种改良的Cornforth-Meyers方法来合成噁唑片段。关键词：卡伊库林，海洋天然产物，磷酸酶抑制剂，全合成，钯催化偶联反应，烯丙基硼化反应，醛缩反应，螺环醚，Cornforth-Meyers噁唑反应。

  DOI：

  10.1139/v01-133

文献信息

• Stereocontrolled synthesis of calyculin A: construction of the C(1)–C(14) tetraene nitrile unit
  作者：Anthony G. M. Barrett、Jeremy J. Edmunds、James A. Hendrix、Kiyoshi Horita、Christopher J. Parkinson

  DOI：10.1039/c39920001238

  日期：——

  An enantioselective and geometrically selective synthesis of the C(1)–C(14) tetraene nitrile unit of calyculin A, using aldol chemistry with (+)-(E)-diisopinocampheylborane and Stille coupling, is described.

  报道了一种利用(+)-(E)-二异松蒎基硼烷和Stille偶联反应，通过aldol反应策略，实现环孢素A的C(1)至C(14)四烯腈单元手性选择性和几何选择性合成的方法。
• Applications of Crotonyldiisopinocampheylboranes in Synthesis:  Total Synthesis of Restrictinol
  作者：Anthony G. M. Barrett、Adrian J. Bennett、Stefan Menzer、Marie L. Smith、Andrew J. P. White、David J. Williams

  DOI：10.1021/jo9815305

  日期：1999.1.1

  The total synthesis of restrictinol, the hydrolysis product of the antifungal natural product restricticin, starting from commercially available methyl (S)-(+)-3-hydroxy-2-methylpropionate is described. Key stages in the strategy involved (i) the use of Brown's allylboration chemistry to construct an acyclic intermediate bearing three of the four stereogenic centers of the natural product, (ii) formation

  描述了从可商购获得的（S）-（+）-3-羟基-2-甲基丙酸甲酯开始的限制素（抗真菌天然产物限制素的水解产物）的全合成。该策略的关键阶段涉及（i）使用Brown的烯丙基硼化化学技术构建一个无环中间体，该中间体带有天然产物的四个立体异构中心中的三个，（ii）形成C-糖苷乙烯基碘，以及（iii）引入三烯侧链通过铃木偶联反应。
• Synthesis of Enantioenriched Propargylic Alcohols Related to Polyketide Natural Products. A Comparison of Methodologies
  作者：James A. Marshall、Matthew P. Bourbeau

  DOI：10.1021/ol034918h

  日期：2003.9.1

  Applications of methodology for the synthesis of propargylic alcohols related to polyketide natural products were examined. Noyori's asymmetric transfer hydrogenation of alpha-chiral alkynones was found to be highly selective and catalyst controlled. Additions of TMS acetylene to alpha-chiral aldehydes, catalyzed by a Ti(O-i-Pr)(4)-BINOL complex, were diastereoselective but substrate dependent.

  [反应：见正文]研究了方法学在合成与聚酮化合物天然产物有关的炔丙醇中的应用。发现Noyori的α-手性炔烃的不对称转移氢化具有很高的选择性和催化剂控制性。由Ti（Oi-Pr）（4）-BINOL配合物催化的TMS乙炔向α-手性醛的加成是非对映选择性的，但取决于底物。
• An enantioselective synthesis of (6R)-lactacystin
  作者：E.J. Corey、Soongyu Choi

  DOI：10.1016/s0040-4039(00)61573-3

  日期：1993.10

  The first enantiospecific, stereocontrolled total synthesis of (6R)-lactacystin, a potential neurotrophic agent, is described.

  描述了第一个对映体特异性，立体控制的（6R）-lactacystin，一种潜在的神经营养剂的总合成。
• Applications of crotyldiisopinocampheylboranes in synthesis: a formal total synthesis of (+)-calyculin A
  作者：Oren P Anderson、Anthony GM Barrett、Jeremy J Edmunds、Shun-Ichiro Hachiya、James A Hendrix、Kiyoshi Horita、James W Malecha、Christopher J Parkinson、Andrew VanSickle

  DOI：10.1139/v01-133

  日期：2001.11.1

  The formal total synthesis of the marine metabolite (+)-calyculin A is reported. The key steps involve (i) the use of Brown allylboration chemistry to control the relative and absolute stereochemistry of homoallylic alcohol arrays, thus setting eight of the desired stereocenters; (ii) Stille coupling methodology in the construction of the cyano tetraene unit of the natural product; and (iii) a modified Cornforth–Meyers approach to the synthesis of the oxazole fragment.Key words: calyculin, marine natural product, phosphatase inhibitor, total synthesis, palladium catalyzed coupling reactions, allylboration reactions, aldol reactions, spiroketal, Cornforth–Meyers oxazole reaction.

  报道了海洋代谢产物（+）-卡伊库林A的正式全合成。关键步骤包括（i）使用布朗烯丙基硼化化学来控制同型烯醇阵列的相对和绝对立体化学，从而设置所需的八个立体中心；（ii）在构建天然产物的氰基四烯单元中使用斯蒂尔偶联方法；以及（iii）一种改良的Cornforth-Meyers方法来合成噁唑片段。关键词：卡伊库林，海洋天然产物，磷酸酶抑制剂，全合成，钯催化偶联反应，烯丙基硼化反应，醛缩反应，螺环醚，Cornforth-Meyers噁唑反应。