[R-(4α,5β)]-4,5-dicyclohexyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane | 393166-59-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: [R-(4α,5β)]-4,5-dicyclohexyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane
• 英文别名: (4R,5R)-4,5-dicyclohexyl-2-(trityloxymethyl)-1,3,2-dioxaborolane
• CAS: 393166-59-1
• 化学式: C₃₄H₄₁BO₃
• 分子量: 508.509
• InChiKey: SKWZLHOVBHDKPN-CZNDPXEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.97
• 重原子数：
  38
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [R-(4α,5β)]-4,5-dicyclohexyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane 在 正丁基锂 、 二异丙胺 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 16.0h， 生成 (4R,5R)-4,5-dicyclohexyl-2-((S)-1-(trityloxy)propan-2-yl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  Callipeltin A受保护侧链的立体选择性合成

  摘要：

  手性硼酸酯的 Matteson 同系物被证明是合成高度官能化的氨基和羟基酸残基的极好工具。该方法提供了直接立体选择性访问 callipeltin A 的侧链，这是一种具有有趣生物活性的天然海产品。此外，该协议应允许在未来的 SAR 研究中改变替换模式，只需在认证步骤中选择合适的亲核试剂即可。

  DOI：

  10.1021/acs.orglett.2c02586
• 作为产物：
  描述：

  4,4,5,5-tetramethyl-2-[(triphenylmethoxy)methyl]-1,3,2-trioxaborolane 、 meso-1,2-dicyclohexyl-ethane-1,2-diol 以 正戊烷 为溶剂， 以98%的产率得到[R-(4α,5β)]-4,5-dicyclohexyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane
  参考文献：
  名称：

  ((Trityloxy)methyl)boronic Esters

  摘要：

  Sodium trityl oxide with 2-(bromomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [pinacol (bromomethyl)boronate (1)] in dimethyl sulfoxide efficiently yields 4,4,5,5-tetramethyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane (3), which can be transesterified with chiral diols to form other [(triphenylmethoxy)methyl]-1,3,2-dioxaborolanes. These can undergo chain extension with (dichloromethyl)lithium in the normal manner and are potentially useful synthetic intermediates. The majority of known boronic esters are liquids, but the trityl group confers crystallinity on several examples. Six structures have been determined: 4,4,5,5-tetramethyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane (3), [R-(4 alpha,5 beta)]-4,5-dicyclohexyl-2-[(triphenylmethoxy)methyl] (4), [S-(4 alpha,5 beta)]-4,5-bis(1-methylethyl)-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane (5), (R)-pinanediol ((trityloxy)methyl)boronate (ent-6), (S)-pinanediol (S)-(1-chloro-2-(trityloxy)ethyl)boronate (7a), and (S)-pinanediol (S)-(1-bromo-2-(trityloxy)ethyl)boronate (7b). The 1,3,2-dioxaborolane ring is very nearly planar, consistent with strong oxygen-boron pi-bonding.

  DOI：

  10.1021/om00006a034

文献信息

• (Alkoxyalkyl)boronic Ester Intermediates for Asymmetric Synthesis
  作者：Donald S. Matteson、Raman Soundararajan、Oliver Chenpu Ho、Winfried Gatzweiler

  DOI：10.1021/om950574q

  日期：1996.1.9

  The use of boronic ester chemistry in the construction of synthetic intermediates containing two or three chiral centers corresponding to steric relationships in the macrolide leuconolide has been explored. A four-carbon chain with a substituent at each carbon has been built from each end, and the effects of different chiral directors and masking groups have been compared. Exceptionally facile debenzylation

  已经研究了硼酸酯化学在构建包含两个或三个手性中心的合成中间体中的应用，所述手性中心对应于大环内酯亮隐内酯中的空间关系。从每个末端构建了一个在每个碳原子上带有取代基的四碳链，并比较了不同手性导向剂和掩蔽基团的作用。已观察到由四个碳原子与硼酸酯官能团隔开的苄氧基极易脱苄基作用，这可能是较早尝试通过类似化学合成糖的尝试失败的原因。已发现在DMSO中用氢化钠将α-氯硼酸酯还原为烷基硼酸酯的新方法。
• Synthesis of HC-Toxin via Matteson Homologation and C–H Functionalization
  作者：Michael Kohr、Uli Kazmaier

  DOI：10.1021/acs.joc.3c00914

  日期：2023.8.4

  host-specific HC-toxin was developed. The HC-toxin belongs to a group of cyclic, tetrapeptide histone deacetylase inhibitors containing the unusual amino acid Aeo. Key steps in the synthesis of this building block include the Matteson homologation to generate the stereogenic centers in the side chain and a C–H functionalization to connect the side chain to a protected alanine.

  开发了一种针对宿主特异性 HC 毒素的新合成路线。HC-毒素属于一组环状四肽组蛋白脱乙酰酶抑制剂，含有不常见的氨基酸 Aeo。合成该结构单元的关键步骤包括用于在侧链中生成立体中心的 Matteson 同系化以及用于将侧链连接到受保护的丙氨酸的 C-H 功能化。
• Total synthesis and biological evaluation of histone deacetylase inhibitor WF-3161
  作者：Michael Kohr、Niklas Papenkordt、Manfred Jung、Uli Kazmaier

  DOI：10.1039/d3ob00641g

  日期：——

  A novel synthesis of the naturally occurring HDAC inhibitor WF-3161 is described. Key steps include the Matteson homologation to generate the stereogenic centres in the side chain, and Pd-catalysed C–H functionalisation to connect the side chain to the peptide backbone. WF-3161 was found to be highly selective for HDAC1, whereas no activity was observed towards HDAC6. High activity was also found against

  描述了天然存在的 HDAC 抑制剂 WF-3161 的新合成。关键步骤包括 Matteson 同源化以在侧链中生成立体中心，以及 Pd 催化的 C-H 功能化以将侧链连接到肽主链。WF-3161 被发现对 HDAC1 具有高度选择性，而对 HDAC6 没有观察到活性。还发现了针对癌细胞系 HL-60 的高活性。
• ((Trityloxy)methyl)boronic Esters
  作者：Oliver C. Ho、Raman Soundararajan、Jianhui Lu、Donald S. Matteson、Zhenming Wang、Xin Chen、Mingyi Wei、Roger D. Willett

  DOI：10.1021/om00006a034

  日期：1995.6

  Sodium trityl oxide with 2-(bromomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [pinacol (bromomethyl)boronate (1)] in dimethyl sulfoxide efficiently yields 4,4,5,5-tetramethyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane (3), which can be transesterified with chiral diols to form other [(triphenylmethoxy)methyl]-1,3,2-dioxaborolanes. These can undergo chain extension with (dichloromethyl)lithium in the normal manner and are potentially useful synthetic intermediates. The majority of known boronic esters are liquids, but the trityl group confers crystallinity on several examples. Six structures have been determined: 4,4,5,5-tetramethyl-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane (3), [R-(4 alpha,5 beta)]-4,5-dicyclohexyl-2-[(triphenylmethoxy)methyl] (4), [S-(4 alpha,5 beta)]-4,5-bis(1-methylethyl)-2-[(triphenylmethoxy)methyl]-1,3,2-dioxaborolane (5), (R)-pinanediol ((trityloxy)methyl)boronate (ent-6), (S)-pinanediol (S)-(1-chloro-2-(trityloxy)ethyl)boronate (7a), and (S)-pinanediol (S)-(1-bromo-2-(trityloxy)ethyl)boronate (7b). The 1,3,2-dioxaborolane ring is very nearly planar, consistent with strong oxygen-boron pi-bonding.
• Stereoselective Synthesis of a Protected Side Chain of Callipeltin A
  作者：Alexander Horn、Uli Kazmaier

  DOI：10.1021/acs.orglett.2c02586

  日期：2022.10.7

  Matteson homologations of chiral boronic esters proved to be an excellent tool for the synthesis of highly functionalized amino and hydroxy acid residues. This method provides straightforward stereoselective access to the side chain of callipeltin A, a natural marine product with interesting biological activities. Furthermore, this protocol should allow for variations in the substitution pattern in

  手性硼酸酯的 Matteson 同系物被证明是合成高度官能化的氨基和羟基酸残基的极好工具。该方法提供了直接立体选择性访问 callipeltin A 的侧链，这是一种具有有趣生物活性的天然海产品。此外，该协议应允许在未来的 SAR 研究中改变替换模式，只需在认证步骤中选择合适的亲核试剂即可。