2-[[(1S,2S)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane | 1417175-76-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: 2-[[(1S,2S)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane
• CAS: 1417175-76-8
• 化学式: C₈H₁₅BO₂
• 分子量: 154.017
• InChiKey: QZWCACMPULDCIZ-JGVFFNPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[[(1S,2S)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane 在 4-二甲氨基吡啶 、 二氯苯酚溴酯 、 potassium carbonate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 生成
  参考文献：
  名称：

  Enantioselective syn and anti Homocrotylation of Aldehydes: Application to the Formal Synthesis of Spongidepsin

  摘要：

  Whereas crotylboration has been a useful method for synthesis of stereochemically complex products, we have shown that homocrotylboration can be achieved with cyclopropanated crotylation reagents, and that the stereo-selectivity of the reaction can be predicted by analogous models. This paper presents a full account of this work, including the first examples of asymmetric anti homocrotylation. The scope of this reaction is demonstrated with highly enantioselective homocrotylation of both aliphatic and aromatic aldehydes, as well as double diastereoselection studies. An application of the synthesis of the marine natural product spongidepsin is presented, as well as streamlined syntheses of homocrotylation reagents.

  DOI：

  10.1021/jacs.5b08858
• 作为产物：
  描述：

  4,4,5,5-Tetramethyl-2-(((1R,2R)-2-methylcyclopropyl)methyl)-1,3,2-dioxaborolane 在 sodium periodate 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 7.83h， 生成 2-[[(1S,2S)-2-methylcyclopropyl]methyl]-1,3,2-dioxaborinane
  参考文献：
  名称：

  Homoallylboration and Homocrotylboration of Aldehydes

  摘要：

  A simple method for addition of homoallylic fragments to aldehydes is described. Cydopropanated allylboration reagents react with aldehydes in the presence of PhBCl2 to give high yields of bishomoallyl alcohols. Cyclopropanated cis- and trans-crotyl reagents afford the corresponding 1,3-anti- and 1,3-syn-methyl-substituted "homocrotylated" alcohols with high selectivity, consistent with a Zimmerman-Traxler transition state. Accordingly, the optically active alpha-substituted reactant affords the E-substituted product in 97:3 er.

  DOI：

  10.1021/ja2048682

文献信息

• A Ring Closing Metathesis Approach to the Formal Synthesis of (+)‐Callyspongiolide
  作者：Kwang‐Yoon Ko、Zoe E. Wilson、Daniel P. Furkert、Margaret A. Brimble

  DOI：10.1002/cctc.202001139

  日期：2020.11.19

  An enantioselective synthesis of macrocyclic core of (+)‐callyspongiolide is described, constituting a formal synthesis of this natural product. The synthetic strategy constructs the 14‐membered macrocyclic domain via Yamaguchi esterification followed by a challenging ring‐closing metathesis (RCM) to effect the final formation of the macrolactone.

  描述了对映体选择性合成（+）-allyspongiolide大环核，构成了该天然产物的形式合成。合成策略是通过Yamaguchi酯化反应构建具有14个成员的大环结构域，然后通过具有挑战性的闭环复分解（RCM）来实现大内酯的最终形成。
• Enantioselective Homocrotylboration of Aliphatic Aldehydes
  作者：Hongkun Lin、Wenbo Pei、Hao Wang、Kendall N. Houk、Isaac J. Krauss

  DOI：10.1021/ja311061n

  日期：2013.1.9

  A practical route to optically pure syn-homocrotylation reagents is described, including highly diastereo- and enantioselective preparation of numerous syn-homocrotyl products, as well as several matched mismatched pairs. NMR experiments suggest that the active homocrotylating species is a cyclopropylcarbinyldichloroborane generated by chloride exchange from the PhBCl2 activator. Computational studies support the intermediacy of chloroboranes and suggest that homoallyl/homocrotyl transfers occur through Zimmerman-Traxler transition states.
• Boron Carboxylate Catalysis of Homoallylboration
  作者：Gabrielle J. Dugas、Yu-hong Lam、K. N. Houk、Isaac J. Krauss

  DOI：10.1021/jo500599h

  日期：2014.5.16

  Boron tris(trifluoroacetate) is identified as the first effective catalyst for the homoallyl- and homocrotylboration of aldehydes by cyclopropylcarbinylboronates. NMR spectroscopic studies and theoretical calculations of key intermediates and transition states both suggest that a ligand-exchange mechanism, akin to our previously reported PhBCl2-promoted homoallylations, is operative. Our experimental and theoretical results also suggest that the catalytic activity of boron tris(trifluoroacetate) might originate from more facile catalytic turnover of the trifluoroacetate ligands (in agreement with DFT calculations) or from a lower propensity for formation of off-pathway reservoir intermediates (as observed by H-1 NMR). This work shows that carboxylates are viable catalytic ligands for homoallyl- and homocrotylations of carbonyl compounds and opens the door to the development of catalytic asymmetric versions of this transformation.