(2R,3S)-3-hydroxy-2-methyl-2-(phenylmethoxymethyl)cyclohexan-1-one | 619335-62-5

• 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: (2R,3S)-3-hydroxy-2-methyl-2-(phenylmethoxymethyl)cyclohexan-1-one
• CAS: 619335-62-5
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: USDMYNDYFQVQOZ-DZGCQCFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S)-3-hydroxy-2-methyl-2-(phenylmethoxymethyl)cyclohexan-1-one 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 13.0h， 生成 (2R,4aR,8aS)-hexahydro-4a-methyl-2-phenylbenzo[d][1,3]dioxin-5-one
  参考文献：
  名称：

  紫杉烷骨架的合成研究：通过分子内B-烷基铃木-宫浦交叉偶联反应构建八元碳环。

  摘要：

  已经研究了通过分子内B-烷基铃木-宫浦交叉偶联反应构建八元碳环的方法。该协议通过以高收率形成在其环上具有季碳原子的八元环而证明了其效力，这为紫杉醇八元环的新进入提供了希望。[反应：看文字]

  DOI：

  10.1021/ol0481939
• 作为产物：
  描述：

  (2,6-dimethoxy-1-methylcyclohexa-2,5-dien-1-yl)methanol 在 盐酸 、 Triton X 、 baker's yeast 、 四丁基碘化铵 、 sodium hydride 、 蔗糖 作用下， 以 四氢呋喃 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 58.25h， 生成 (2R,3S)-3-hydroxy-2-methyl-2-(phenylmethoxymethyl)cyclohexan-1-one
  参考文献：
  名称：

  Preparation of new chiral building blocks via asymmetric catalysis

  摘要：

  Highly enantio- and stereoselective preparation of some new chiral building blocks with baker's yeast or the CBS catalyst is described. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.009

文献信息

• Formal Total Synthesis of (−)-Taxol through Pd-Catalyzed Eight-Membered Carbocyclic Ring Formation
  作者：Sho Hirai、Masayuki Utsugi、Mitsuhiro Iwamoto、Masahisa Nakada

  DOI：10.1002/chem.201404295

  日期：2015.1.2

  A formal total synthesis of (−)‐taxol by a convergent approach utilizing Pd‐catalyzed intramolecular alkenylation is described. Formation of the eight‐membered carbocyclic ring has been a problem in the convergent total synthesis of taxol but it was solved by the Pd‐catalyzed intramolecular alkenylation of a methyl ketone affording the cyclized product in excellent yield (97 %), indicating the high

  描述了通过聚合方法利用钯催化的分子内烯基化的形式正式合成（-）-紫杉醇。八元碳环的形成一直是紫杉醇聚合全合成中的一个问题，但已通过Pd催化的甲基酮分子内烯基化反应得以解决，从而以优异的收率（97％）提供了环化产物，表明该方法具有较高的收率。钯催化的分子内烯基化反应 发现环氧苄醚通过1,5-氢化物移位进行重排，生成C3立体异构中心，随后形成C1-C2苄叉，并用于制备Pd催化反应的底物。
• Development of silicon-tethered anionic reaction and its application to the synthesis of chiral A-ring moieties of Taxol™
  作者：Mitsuhiro Iwamoto、Masayuki Miyano、Masayuki Utsugi、Hatsuo Kawada、Masahisa Nakada

  DOI：10.1016/j.tetlet.2004.09.143

  日期：2004.11

  Silicon-tethered intramolecular nucleophilic additions of a hydroxymethyl unit to ketones in β-hydroxyketones have been developed. The product obtained by this protocol was successfully converted to chiral A-ring moieties of Taxol™. Also developed was a promising silicon-tethered intramolecular α-alkylation reaction of the cyclic hydroxyketone.

  已经开发了羟基甲基单元的硅拴分子内亲核加成物到β-羟基酮中的酮上。通过该方案获得的产物已成功转化为Taxol™的手性A环部分。还开发了有希望的环状羟基酮的硅系分子内α-烷基化反应。
• Enantioselective Total Synthesis of (+)-Bucidarasins A and C
  作者：Masahisa Nakada、Kenji Usui

  DOI：10.3987/com-14-13161

  日期：——

  In this paper, the first total synthesis of (+)-bucidarasins A and C is described. The chiral starting material was successfully obtained via reduction using a CBS catalyst and selective mono-TBS ether formation of trans-2-benzyloxymethy1-2-methylcyclohexane-1,3-diol, which was crucial to the successful enantioselective total synthesis of (+)-bucidarasins A and C. A synthetic approach towards (+)-bucidarasin C, based on the Barton-McCombie protocol, using V-70 as a radical promoter at low temperature to remove the C6-hydroxy moiety is also described.
• Synthetic studies on (+)-bucidarasin C: two diastereoselective transannular reactions producing cis-decaline derivatives that show reversal selectivity
  作者：Akinobu Nakahara、Misaki Kanbe、Masahisa Nakada

  DOI：10.1016/j.tetlet.2012.01.058

  日期：2012.3

  This manuscript describes studies on the construction of the cis-decaline core of (+)-bucidarasin C. The transannular Diels-Alder (TADA) reaction of a macrocyclic lactone successfully afforded the desired cis-decaline derivative in a stereoselective manner. On the other hand, the stereoselective transannular cascade Michael (TACM) reaction of the parent macrocyclic lactone afforded the diastereomeric cis-decaline derivative as the major product. (C) 2012 Elsevier Ltd. All rights reserved.