(S)-(+)-2-(2-(4-methoxyphenyl)propyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1262985-44-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (S)-(+)-2-(2-(4-methoxyphenyl)propyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-[(2S)-2-(4-methoxyphenyl)propyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；2-(2-(4-methoxyphenyl)propyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1262985-44-3
• 化学式: C₁₆H₂₅BO₃
• 分子量: 276.184
• InChiKey: VLXIDYTVGAIIPE-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  (S)-(+)-2-(2-(4-methoxyphenyl)propyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 双氧水 、 potassium hydroxide 、 四溴化碳 、 三苯基膦 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  钴催化的最小官能化异构烯烃的对映收敛加氢

  摘要：

  由于对映体纯化合物的高需求，烯烃不对称氢化的研究在药物分子合成和化学工业中都具有重要意义。已建立的方法通常需要几何纯烯烃。对映收敛反应提供了通过氢化E / Z -烯烃混合物获得单一立体异构体的可能性；然而，通常需要在碳-碳双键旁边的极性官能团。在这里，我们报道了一种钴催化的对映收敛氢化容易获得的最小官能化E / Z-烯烃混合物。该策略显示出良好的官能团耐受性，并为对映收敛转化提供了一种替代方法。初步机理研究表明，钴催化异构化是实现收敛转化的关键。

  DOI：

  10.1021/jacs.2c08525
• 作为产物：
  描述：

  在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 4.83h， 生成 (S)-(+)-2-(2-(4-methoxyphenyl)propyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Toward Ideality: The Synthesis of (+)-Kalkitoxin and (+)-Hydroxyphthioceranic Acid by Assembly-Line Synthesis

  摘要：

  The iterative homologation of boronic esters using chiral lithiated benzoate esters and chloromethyllithium has been applied to the highly efficient syntheses of two natural products, (+)-kalkitoxin and (+)-hydroxyphthioceranic acid. The chiral lithiated benzoate esters (>99% ee) were generated from the corresponding stannanes, which themselves were prepared by HoppeBeak deprotonation of ethyl 2,4,6-triisopropyl-benzoate with s-BuLi in the presence of (+)- or (-)-sparteine and trapping with Me3SnCl followed by recrystallization. In addition, it was found that purification between several homologations could be avoided, substantially increasing both chemical and manpower efficiency. In the case of (+)-kalkitoxin, six iterative homologations were conducted on commercially available p-MeOC(6)H(4)CH(2)Bpin to build up the core of the molecule before the C-B bond was converted into the desired CN bond, without purification of intermediates. In the case of (+)-hydroxyphthioceranic acid, 16 iterative homologations were conducted on p-MeOC(6)H(4)Bpin with only four intermediate purifications before oxidation of the C-B bond to the desired alcohol. The stereocontrolled and efficient syntheses of these complex molecules highlight the power of iterative chemical synthesis using boronic esters.

  DOI：

  10.1021/ja512875g

文献信息

• Enantioselective Copper-Catalyzed Methylboration of Alkenes
  作者：Bin Chen、Peng Cao、Yang Liao、Min Wang、Jian Liao

  DOI：10.1021/acs.orglett.7b03860

  日期：2018.3.2

  on (B2(pin)2), and methyl iodide is reported. Alkenes including styrenes, β-substituted styrenes, and challenging aliphatic olefins were smoothly transferred to the desired methylboration products with excellent diastereoselectivities (dr up to >99:1) and enantioselectivities (er up to 99:1). The utility of this process was demonstrated by the synthesis of naproxen and formal synthesis of two natural

  据报道，烯烃，双（频哪醇）二硼（B 2（pin）2）和甲基碘的对映选择性铜催化的硼酸酯交叉偶联反应。将包括苯乙烯，β-取代苯乙烯和挑战性脂肪族烯烃在内的烯烃平稳地转移到所需的甲基硼酸酯产品中，该产品具有出色的非对映选择性（dr高达> 99：1）和对映选择性（er高达99：1）。萘普生的合成和两种天然产物的正式合成证明了该方法的实用性。
• Iminopyridine Oxazoline Iron Catalyst for Asymmetric Hydroboration of 1,1-Disubtituted Aryl Alkenes
  作者：Jianhui Chen、Tuo Xi、Zhan Lu

  DOI：10.1021/ol503282r

  日期：2014.12.19

  The highly regio- and enantioselective iron-catalyzed anti-Markovnikov hydroboration of 1,1-disubstituted aryl alkenes is reported by using a novel chiral iminopyridine oxazoline (IPO) ligand, in which the iminopyridine group is proposed to stabilize the iron and chiral oxazoline group to control enantioselectivity. This distinct class of reactive IPO ligands will likely be of high value for a large

  通过使用新型手性亚氨基吡啶恶唑啉（IPO）配体报道了高度区域和对映选择性的铁催化的1,1-二取代芳基烯烃的反马尔科夫尼科夫硼氢化反应，其中建议使用亚氨基吡啶基团来稳定铁和手性恶唑啉基团控制对映选择性。对于使用第一行过渡金属进行的各种不对称转化，这种独特的反应性IPO配体类别可能具有很高的价值。
• Highly regio- and enantioselective catalytic asymmetric hydroboration of α-substituted styrenyl derivatives
  作者：Clément Mazet、David Gérard

  DOI：10.1039/c0cc01547d

  日期：——

  The catalytic asymmetric hydroboration of a variety of 1,1-disubstituted olefins has been achieved with excellent yields, perfect regioselectivity and in some cases, high levels of enantioselectivity using readily accessible iridium catalyst.

  使用容易获得的铱催化剂，已经以优异的收率，完美的区域选择性以及在某些情况下高水平的对映选择性实现了各种1,1-二取代烯烃的催化不对称硼氢化反应。
• Selective uni- and bidirectional homologation of diborylmethane
  作者：Daniel J. Blair、Damiano Tanini、Joseph M. Bateman、Helen K. Scott、Eddie L. Myers、Varinder K. Aggarwal

  DOI：10.1039/c6sc05338f

  日期：——

  carbenoid, which can be a sparteine-ligated or a diamine-free lithiated benzoate/carbamate. The scope of the 1,2-bis(boronic esters) so generated is complementary to that encompassed by the asymmetric diboration of alkenes, in that primary–secondary and primary–tertiary 1,2-bis(boronic esters) can be prepared with equally high levels of selectivity and that functional groups, such as terminal alkynes and alkenes

  通过使用对映体纯的锂稳定类胡萝卜素，二硼基甲烷可以单向和双向同系化，分别得到 1,2- 和 1,3- 双（硼酸酯），收率良好，并且具有优异的对映选择性和非对映选择性。转换对空间位阻的高敏感性使得任一歧管都能单独操作，这通过明智地选择类胡萝卜素类型来实现，类胡萝卜素可以是金雀花碱连接的或不含二胺的锂化苯甲酸酯/氨基甲酸酯。如此生成的 1,2-双（硼酸酯）的范围与烯烃的不对称二硼化所涵盖的范围是互补的，因为伯-仲和伯-叔 1,2-双（硼酸酯）可以同样地制备高水平的选择性，并且可以耐受末端炔烃和烯烃等官能团。还描述了形成C 2 -对称和非对称反式和顺式1,3-双（硼酸酯）的方法，并且代表了获得1,3-官能化合成中间体的有力途径。