(2R,3R,4R)-4-(tert-butyldimethylsiloxy)-3-methoxy-2-methylpentanal | 177598-65-1

• 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: (2R,3R,4R)-4-(tert-butyldimethylsiloxy)-3-methoxy-2-methylpentanal
• 英文别名: (2R,3R,4R)-4-(tert-butyldimethylsilyloxy)-3-methoxy-2-methylpentanal；(2R,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-3-methoxy-2-methylpentanal
• CAS: 177598-65-1
• 化学式: C₁₃H₂₈O₃Si
• 分子量: 260.449
• InChiKey: ZFCJBHUEVACYAO-QJPTWQEYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R)-4-(tert-butyldimethylsiloxy)-3-methoxy-2-methylpentanal 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 盐酸 、 叔丁基过氧化氢 、 锂硼氢 、 四(三苯基膦)钯 、 正丁基锂 、 氯化亚砜 、 bis(acetylacetonate)oxovanadium 、 水 、 sodium hexamethyldisilazane 、 caesium carbonate 、 戴斯-马丁氧化剂 、 三甲基氢氧化锡 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 1,1-二氯乙烷 、 正己烷 、 二氯甲烷 、 水 、 丙酮 、 苯 为溶剂， 反应 55.67h， 生成 3-{[(6,7-二乙氧基-1,2,3,4-四氢萘-2-基)氨基]甲基}-6-(乙烯氧基)环己-2,4-二烯-1-酮盐酸
  参考文献：
  名称：

  A Stereoselective Synthesis of (+)-Herboxidiene/GEX1A

  摘要：

  A stereoselective synthesis of (+)-herboxidiene is described. The convergent synthesis utilized a Suzuki cross-coupling reaction to assemble the key segments. The synthesis of the functionalized tetrahydropyran ring utilized an Achmatowicz reaction as the key step. The synthesis of the C10-C19 segment was accomplished using Brown's crotylboration, asymmetric alkylation, and a stereoselective allylic chlorination reactions.

  DOI：

  10.1021/ol102549a
• 作为产物：
  描述：

  (2R,3R,4S)-2-hydroxy-3-methoxy-4-methylhex-5-enyl 4-methylbenzenesulfonate 在 吡啶 、 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 1.08h， 生成 (2R,3R,4R)-4-(tert-butyldimethylsiloxy)-3-methoxy-2-methylpentanal
  参考文献：
  名称：

  A Stereoselective Synthesis of (+)-Herboxidiene/GEX1A

  摘要：

  A stereoselective synthesis of (+)-herboxidiene is described. The convergent synthesis utilized a Suzuki cross-coupling reaction to assemble the key segments. The synthesis of the functionalized tetrahydropyran ring utilized an Achmatowicz reaction as the key step. The synthesis of the C10-C19 segment was accomplished using Brown's crotylboration, asymmetric alkylation, and a stereoselective allylic chlorination reactions.

  DOI：

  10.1021/ol102549a

文献信息

• A Formal Synthesis of Herboxidiene/GEX1A
  作者：Jhillu S. Yadav、G. Madhusudhan Reddy、S. Rehana Anjum、B. V. Subba Reddy

  DOI：10.1002/ejoc.201402235

  日期：2014.7

  A formal synthesis of herboxidiene/GEX 1A is described. This approach demonstrates successful application of the Prins cyclization for the construction of the tetrahydropyran core of the target molecule. The chirality of the side chain has been established through the Sharpless asymmetric dihydroxylation and Evan's alkylation. The olefin cross-metathesis was applied to couple both key fragments.

  描述了herboxidiene/GEX 1A 的正式合成。这种方法证明了 Prins 环化在构建目标分子的四氢吡喃核心中的成功应用。侧链的手性是通过 Sharpless 不对称二羟基化和 Evan 烷基化建立的。应用烯烃交叉复分解来偶联两个关键片段。
• Synthetic studies on the rhizoxins. II. An approach to the C10C26 subunit using “substrate directed” allylstannane additions to aldehydes
  作者：Gary E Keck、Kenneth A Savin、Michael A Weglarz、Erik N.K Cressman

  DOI：10.1016/0040-4039(96)00578-3

  日期：1996.5

  The construction of a C10C26 fragment of the 16-membered antitumor macrolide rhizoxin has been achieved in an efficient manner. The central portion of this molecule has been prepared in enantiopure form via an iterative allylstannylation protocol starting with the ester of (R)-lactic acid. The oxazole portion of rhizoxin was attached via a samarium diiodide modified Julia coupling to generate the

  一个C的结构10 C 26的16-元大环内酯抗肿瘤根瘤菌素片段具有以有效的方式实现。该分子的中心部分已通过对映异构纯的形式，从（R）-乳酸的酯开始，通过重复的烯丙基甲磺酰化方法制备。经由二碘化sa改性的Julia偶联连接了根霉菌素的恶唑部分，以产生所需的全部E三烯。
• A Total Synthesis of Herboxidiene Methyl Ester
  作者：Martin G. Banwell、Rajaratnam Premraj、Malcolm D. McLeod、Gregory W. Simpson

  DOI：10.3987/com-12-12597

  日期：——

  The total synthesis of the methyl ester, 35, of herboxidiene (1, a.k.a. GEX1A and TAN-1609), a polyketide displaying both herbicidal and anti-tumor activity, is described. The convergent reaction sequence involves, in its closing stages, the union of the phosphine oxide 3 with the aldehyde 21 to deliver, via a Horner-Wittig reaction with accompanying epimerization at C12, compound 33 that after deprotection affords an alcohol, 34, capable of participating in a regio- and diastereo-selective epoxidation reaction to give target 35. Phosphine oxide 3 was prepared via the intramolecular hetero-Michael addition of a secondary alcohol to a tethered and Z-configured acrylate while aldehyde 21 was generated, in the crucial step of the relevant reaction sequence, via an Ireland-Claisen rearrangement reaction.
• A Stereoselective Synthesis of (+)-Herboxidiene/GEX1A
  作者：Arun K. Ghosh、Jianfeng Li

  DOI：10.1021/ol102549a

  日期：2011.1.7

  A stereoselective synthesis of (+)-herboxidiene is described. The convergent synthesis utilized a Suzuki cross-coupling reaction to assemble the key segments. The synthesis of the functionalized tetrahydropyran ring utilized an Achmatowicz reaction as the key step. The synthesis of the C10-C19 segment was accomplished using Brown's crotylboration, asymmetric alkylation, and a stereoselective allylic chlorination reactions.