(2R,3R)-3-Hydroxy-2-methyl-2-(2-methyl-allyl)-cyclopentanone | 109120-87-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R)-3-Hydroxy-2-methyl-2-(2-methyl-allyl)-cyclopentanone
• 英文别名: (2R,3R)-3-hydroxy-2-methyl-2-(2-methylprop-2-enyl)cyclopentan-1-one
• CAS: 109120-87-8
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: RGXMRVWAYISLTG-PSASIEDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-甲基-1,3-环戊二酮 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 生成 (2R,3R)-3-Hydroxy-2-methyl-2-(2-methyl-allyl)-cyclopentanone
  参考文献：
  名称：

  Asymmetric microbial reduction of prochiral 2,2,-disubstituted cycloalkanediones

  摘要：

  DOI：

  10.1021/jo00391a009

文献信息

• Enantioselective total synthesis of (-)-subergorgic acid
  作者：Leo A. Paquette、Philip G. Meister、Dirk Friedrich、Daryl R. Sauer

  DOI：10.1021/ja00054a007

  日期：1993.1

  A completely stereocontrolled total synthesis of (-)-subergorgic acid (1) has been accomplished. The starting β-hydroxy ketone was prepared in optically pure condition by lipase-promoted hydrolysis of the racemic chloroacetate.Ring A was introduced by a reaction sequence that included a Mukaiyama-type aldol condensation and subsequent photochemical oxidation with (diacetoxyiodo)benzene and iodine.

  已经完成了（-）-次高酸（1）的完全立体控制的全合成。起始 β-羟基酮是在光学纯条件下通过脂肪酶促进的外消旋氯乙酸酯水解制备的。通过包括 Mukaiyama 型羟醛缩合和随后用（二乙酰氧基碘）苯和碘进行光化学氧化的反应序列引入环 A。为了允许在环 C 内进行适当的官能化，通过 Pd(II) 促进的衍生烯醇三氟甲磺酸酯与甲酸离子的还原，将羰基转化为内部双键
• Desymmetrization of cyclic 1,3-diketones <i>via</i> Ir-catalyzed hydrogenation: an efficient approach to cyclic hydroxy ketones with a chiral quaternary carbon
  作者：Quan Gong、Jialin Wen、Xumu Zhang

  DOI：10.1039/c9sc01769k

  日期：——

  We herein report an efficient method to synthesize cyclic hydroxy ketones with a chiral quaternary center. Catalyzed by an Ir/f-ampha complex, cyclic α,α-disubstituted 1,3-diketones were hydrogenated, giving mono-reduced products with both high enantioselectivities and diastereoselectivities. In addition, CC and CC bonds could survive in this catalytic system. This method was applied in the preparation

  我们在此报告了一种合成具有手性季铵中心的环状羟基酮的有效方法。在 Ir/f-ampha 配合物的催化下，环状 α,α-二取代 1,3-二酮被氢化，得到具有高对映选择性和非对映选择性的单还原产物。此外，C C 和 C C 键可以在该催化体系中存活。该方法用于制备(+)-雌酮。在这种化学转化中没有观察到二醇。由于空间位阻，实现了对映异构体和非对映异构体的诱导。
• Chiral base mediated transformation of cyclic 1,3-diketones
  作者：Benjamin Butler、Thomas Schultz、Nigel S. Simpkins

  DOI：10.1039/b606864b

  日期：——

  Treatment of certain 1,3-diketones with a chiral lithium amide base results in the formation of a non-racemic lithium mono-enolate; these intermediates can be transformed directly into chiral hydroxyketone products by reduction with DIBAL-H in high yield and with selectivities of up to 99% ee.

  用手性锂酰胺碱处理某些1,3-二酮会导致形成非外消旋单烯酸锂。这些中间体可以通过用DIBAL-H还原并以高达99％ee的选择性直接转化为手性羟基酮产物。
• CuH-Catalyzed Enantioselective Desymmetrization of Cyclic 1,3-Diketones
  作者：Vaibhav B. Patil、Sandip B. Jadhav、Jagadeesh Babu Nanubolu、Rambabu Chegondi

  DOI：10.1021/acs.orglett.2c03359

  日期：2022.11.11

  cyclopentane-1,3-diones to access cyclic 3-hydroxy ketones having an all-carbon quaternary center with high diastereoselectivity via hydrosilylation using PMHS as an inexpensive hydride source. This reaction displays high functional group tolerance including reducible alkyne, alkene, and ester groups with a broad substrate scope. The importance of chiral cyclic 3-hydroxy ketone building blocks was also demonstrated

  在此，我们报告了 CuH 催化的前手性环戊烷-1,3-二酮的不对称去对称化，使用 PMHS 作为廉价的氢化物源，通过氢化硅烷化反应获得具有全碳季中心和高非对映选择性的环状 3-羟基酮。该反应显示出高官能团耐受性，包括具有广泛底物范围的可还原炔烃、烯烃和酯基团。手性环状 3-羟基酮结构单元的重要性也通过 (-)-雌酮、毒柯烯烷 E 核心和稠合吲哚的合成得到证明。