4,4,5,5-tetramethyl-2-(prop-2-yn-1-yl)-1,3,2-dioxaborolane | 1337935-39-3

• 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: 4,4,5,5-tetramethyl-2-(prop-2-yn-1-yl)-1,3,2-dioxaborolane
• 英文别名: propargylboronic acid pinacol ester；4,4,5,5-tetramethyl-2-prop-2-ynyl-1,3,2-dioxaborolane
• CAS: 1337935-39-3
• 化学式: C₉H₁₅BO₂
• 分子量: 166.028
• InChiKey: SMCYVMQKKOBMIO-UHFFFAOYSA-N

物化性质

• 沸点：
  172.4±23.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.71
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  4,4,5,5-tetramethyl-2-(prop-2-yn-1-yl)-1,3,2-dioxaborolane 在 potassium tert-butylate 作用下， 以 N,N-二甲基甲酰胺-d7 为溶剂， 反应 4.0h， 生成 2-丙二烯基-4,4,5,5-四甲基-1,3,2-二氧杂硼烷
  参考文献：
  名称：

  N-磺酰基酮亚胺的银催化对映选择性炔丙基化反应

  摘要：

  描述了N-磺酰基酮亚胺的对映选择性银催化的炔丙基化。该反应以高收率和优异的对映体比率进行，并且与多种二芳基-和烷基酮亚胺相容。通过炔烃闭环复分解，Sonogashira交叉偶联和还原反应进行的同炔丙基产物的合成转化以高立体化学保真度进行。烯丙基和炔丙基硼烷试剂均可用于获得均炔丙基产物，其分布与涉及用硼烷试剂对银催化剂进行重金属化的机理最一致。

  DOI：

  10.1021/acs.orglett.5b02692
• 作为产物：
  描述：

  碘甲基硼酸频哪醇酯 、 乙炔基溴化镁 以 四氢呋喃 为溶剂， 以20%的产率得到4,4,5,5-tetramethyl-2-(prop-2-yn-1-yl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  N-磺酰基酮亚胺的银催化对映选择性炔丙基化反应

  摘要：

  描述了N-磺酰基酮亚胺的对映选择性银催化的炔丙基化。该反应以高收率和优异的对映体比率进行，并且与多种二芳基-和烷基酮亚胺相容。通过炔烃闭环复分解，Sonogashira交叉偶联和还原反应进行的同炔丙基产物的合成转化以高立体化学保真度进行。烯丙基和炔丙基硼烷试剂均可用于获得均炔丙基产物，其分布与涉及用硼烷试剂对银催化剂进行重金属化的机理最一致。

  DOI：

  10.1021/acs.orglett.5b02692

文献信息

• Highly diastereoselective synthesis of enantioenriched <i>anti</i>-α-allyl-β-fluoroamines
  作者：Philip J. Chevis、Sirilak Wangngae、Thanaphat Thaima、Anthony W. Carroll、Anthony C. Willis、Mookda Pattarawarapan、Stephen G. Pyne

  DOI：10.1039/c9cc02765c

  日期：——

  A highly diastereoselective synthesis of anti-α-allyl-β-fluoroamines has been developed involving enantioselective α-fluorination of aldehydes followed by a diastereoselective Petasis allyl borono-Mannich reaction. The products are obtained generally in good overall yields for the two steps and with drs of 97 : 3–99 : 1 and ees of 86–92%. Selected products were converted to 3-, 5- and 6-membered ring

  已经开发了抗-α-烯丙基-β-氟胺的高度非对映选择性的合成，包括醛的对映选择性α-氟化，然后进行非对映选择性的Petasis烯丙基硼烷-曼尼希反应。通常，两步获得的产品收率均良好，drs为97：3–99：1，ee为86-92％。将选择的产物转化为3、5和6元环杂环，后两种结合有外环氟。
• Visible-Light-Driven α-Substituted Amines Enabled by <i>In Situ</i> Formation of Amine Substrate Aggregates
  作者：Yuqian Zhao、Xiaoli Hou、Min He、Yi Wang、Shilei Yang、Wanhui Wang、Ming Bao、Xiaoqiang Yu

  DOI：10.1021/acs.orglett.3c02826

  日期：2023.10.13

  air-promoted, α-substituted reaction of amines with varying nucleophiles is described. The amine substrate aggregates formed in situ through physical π–π stacking by H2O regulation in organic solvent can absorb visible light and then generate iminium ion intermediates, which undergo nucleophilic substitution reactions with varying nucleophiles to afford α-substituted amines. This reaction features catalyst-free

  描述了胺与不同亲核试剂的可见光驱动、无光催化剂、空气促进、α-取代反应。在有机溶剂中通过H 2 O调节物理π-π堆积而原位形成的胺底物聚集体可以吸收可见光，然后生成亚胺离子中间体，该中间体与不同的亲核试剂发生亲核取代反应，得到α-取代胺。该反应具有无催化剂、官能团耐受性好、操作流程简单、反应条件绿色等特点。
• Zinc-Catalyzed Allenylations of Aldehydes and Ketones
  作者：Daniel R. Fandrick、Jaideep Saha、Keith R. Fandrick、Sanjit Sanyal、Junichi Ogikubo、Heewon Lee、Frank Roschangar、Jinhua J. Song、Chris H. Senanayake

  DOI：10.1021/ol202343c

  日期：2011.10.21

  The general zinc-catalyzed allenylation of aldehydes and ketones with an allenyl boronate Is presented. Preliminary mechanistic studies support a kinetically controlled process wherein, after a site-selective Ban exchange to generate a propargyl zinc intermediate, the addition to the electrophile effectively competes with propargyl-allenyl zinc equilibration. The utility of the methodology was demonstrated by application to a rhodium-catalyzed [4 + 2] cycloaddition.
• NHC–Cu-Catalyzed Addition of Propargylboron Reagents to Phosphinoylimines. Enantioselective Synthesis of Trimethylsilyl-Substituted Homoallenylamides and Application to the Synthesis of <i>S</i>-(−)-Cyclooroidin
  作者：Nicholas W. Mszar、Fredrik Haeffner、Amir H. Hoveyda

  DOI：10.1021/ja500373s

  日期：2014.3.5

  A catalytic method for the efficient and enantioselective addition of a 1-trimethylsilyl-substituted allene moiety to phosphinoylimines is presented. Transformations are promoted by 5.0 mol % of a copper complex of an N-heterocyclic carbene in the presence of a propargylboron reagent that can be readily prepared in multigram quantities. Within 10 min of reaction, products are obtained in up to 91% yield, 98% allene (vs propargyl) selectivity, and 98:2 enantiomeric ratio. An assortment of aldimines serve as suitable substrates. The phosphinoyl and silyl groups can be removed efficiently and orthogonally. The silylallene moiety may be transformed to versatile derivatives that are difficult to access via nonsilylated allenes. The special features and utility of the approach are highlighted through a succinct enantioselective synthesis of marine alkaloid S-(-)-cyclooroidin.
• Copper-Catalyst-Controlled Site-Selective Allenylation of Ketones and Aldehydes with Propargyl Boronates
  作者：Keith R. Fandrick、Junichi Ogikubo、Daniel R. Fandrick、Nitinchandra D. Patel、Jaideep Saha、Heewon Lee、Shengli Ma、Nelu Grinberg、Carl A. Busacca、Chris H. Senanayake

  DOI：10.1021/ol400124f

  日期：2013.3.15

  A practical and highly site-selective copper-PhBPE-catalyst-controlled allenylation with propargyl boronates has been developed. The methodology has shown to be tolerant of diverse ketones and aldehydes providing the allenyl adducts in high selectivity. The BPE ligand and boronate substituents were shown to direct the site selectivity for which either propargyl or allenyl adducts can be acquired in high selectivity. A model is proposed that explains the origin of the site selectivity.