dimethyl(phenyl)(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane | 401513-48-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: dimethyl(phenyl)(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane
• 英文别名: (Me2PhSi)CHCHCH2(B(pin))；(dimethylphenylsilyl)allyl (pinacolato)boronate；Dimethyl-phenyl-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enyl]silane；dimethyl-phenyl-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enyl]silane
• CAS: 401513-48-2
• 化学式: C₁₇H₂₇BO₂Si
• 分子量: 302.297
• InChiKey: CQOMLSRYQSUSII-UHFFFAOYSA-N

物化性质

• 沸点：
  341.3±42.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  dimethyl(phenyl)(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane 在 碘代三甲硅烷 、 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 (E)-1-Phenyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-but-3-en-1-ol
  参考文献：
  名称：

  1-Silyl-1-boryl-2-alkenes: Reagents for Stereodivergent Allylation Leading to 4-Oxy-(E)-1-alkenylboronates and 4-Oxy-(Z)-1-alkenylsilanes

  摘要：

  Silylboryl reagents for organic synthesis: 1-silyl-1-boryl-2-alkenes (2) were prepared efficiently by gem-silylborylation of α-chloroallyllithium compounds from (dimethylphenylsilyl)(pinacolato)borane (1; see scheme, LDA=lithium diisopropylamide) and were demonstrated to allylate acetals and aldehydes in the presence of a Lewis acid to produce (E)-4-alkoxy-alkenylboronates. Heating the reagents with aldehydes in the absence of Lewis acid afforded (Z)-4-hydroxy-alkenylsilanes stereospecifically.

  DOI：

  10.1002/1521-3773(20011119)40:22<4283::aid-anie4283>3.0.co;2-3
• 作为产物：
  描述：

  3-(phenyldimethylsilyl)prop-2-yn-1-ol 在 N-氯代丁二酰亚胺 、 potassium tert-butylate 、 1,3-bis(2,4,6-trimethylphenyl)-imidazolium 、 三苯基膦 、 红铝 、 copper(l) chloride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 12.25h， 生成 dimethyl(phenyl)(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)silane
  参考文献：
  名称：

  配体骨架上的空间调节剂构象固定手性双膦配体：应变 1,2-二取代手性顺式环丙烷的选择性合成

  摘要：

  已经开发了一系列新的 ( R ) -5,8- Si - Quinox - t Bu 3类型的C 1 -对称 P-手性双膦配体（甲硅烷基 = SiMe 3，SiEt 3，SiMe 2 Ph）。与配体主链相连的庞大的甲硅烷基调节剂固定膦取代基，形成可用于底物识别的刚性手性环境。该配体在铜 (I) 催化的大型甲硅烷基取代的烯丙基亲电试剂的不对称硼基环丙烷化方面表现出高性能，可提供比其他可能的异构体反式更高的 1,2-顺式-甲硅烷基-硼基-环丙烷。-环丙烷和烯丙基硼酸酯（高达 97% 的产率；98% ee；顺式/反式= >99:1；环丙烷/烯丙基硼酸酯 = >99:1）。详细的计算研究表明，高度刚性的膦构象几乎不受与庞大的甲硅烷基取代的烯丙基亲电试剂的空间相互作用的干扰，是高立体选择性和产物选择性的关键。此外，详细的计算分析提供了对分子内环化中手性烷基铜 (I) 中间体的立体保留或反转机制的深入了解。

  DOI：

  10.1021/jacs.2c02745

文献信息

• Kinetic Resolution of α‐Silyl‐Substituted Allylboronate Esters via Chemo‐ and Stereoselective Allylboration of Aldehydes
  作者：Jinyoung Park、Yongsuk Jung、Jeongho Kim、Eunsung Lee、Sarah Yunmi Lee、Seung Hwan Cho

  DOI：10.1002/adsc.202001170

  日期：2021.4.27

  We describe the kinetic resolution of α‐silyl‐substituted allylboronate esters via chiral phosphoric acid‐catalyzed chemo‐, diastereo‐ and enantioselective allylboration of aldehydes. This process provides two synthetically versatile enantioenriched compounds, (Z)‐δ‐silyl‐substituted anti‐homoallylic alcohols and α‐silyl‐substituted allylboronate esters, with a selectivity factor up to 328. We propose

  我们描述了通过手性磷酸催化醛的化学，非对映和对映选择性烯丙基硼化反应，α-甲硅烷基取代的烯丙基硼酸酯的动力学拆分。该方法提供了两种合成上通用的对映体富集化合物，（Z）-δ-甲硅烷基取代的抗-均烯丙基醇和α-甲硅烷基取代的烯丙基硼酸酯，选择性高达328。例如，硅烷部分占据伪轴向位置的过渡态，因此很容易拆分α-甲硅烷基取代的烯丙基硼酸酯。获得的对映体富集的化合物的合成效用通过其进一步的转化而突出，以给出多种对映体富集的分子。
• Additions of functionalized α-substituted allylboronates to aldehydes under the novel Lewis and Brønsted acid catalyzed manifolds
  作者：Lisa Carosi、Hugo Lachance、Dennis G. Hall

  DOI：10.1016/j.tetlet.2005.10.115

  日期：2005.12

  stereo- and chemoselectivity in the additions of four model α-substituted allylboronates to benzaldehyde was examined under the standard thermal (uncatalyzed) conditions and the novel Lewis and Brønsted acid-catalyzed conditions. With either of Sc(OTf)3 or triflic acid as catalysts, an α-ethyl allylboronate, 1a, led to a surprising inversion of stereoselectivity that can be tentatively rationalized through

  在标准的热（未催化）条件和新型的路易斯和布朗斯台德酸催化的条件下，考察了向苯甲醛中添加四种模式α-取代的烯丙基硼酸酯到苯甲醛中的立体和化学选择性。使用Sc（OTf）3或三氟甲磺酸作为催化剂，α-乙基烯丙基硼酸酯1a会导致令人惊讶的立体选择性反转，可以通过未催化途径和催化途径之间的烯丙基硼化过渡态几何形状的细微差异来初步合理化。还发现α-甲硅烷基试剂的化学选择性（1c和1d可以在使用催化剂时逆转，从而提供烯丙基甲硅烷基化产物而不是由热未催化反应获得的烯丙基硼化产物。
• Iridium‐Catalyzed Chemo‐, Diastereo‐, and Enantioselective Allyl‐Allyl Coupling: Accessing All Four Stereoisomers of ( <i>E</i> )‐1‐Boryl‐Substituted 1,5‐Dienes by Chirality Pairing
  作者：Yongsuk Jung、Seok Yeol Yoo、Yonghoon Jin、Jaehyun You、Seungcheol Han、Jeongwoo Yu、Yoonsu Park、Seung Hwan Cho

  DOI：10.1002/anie.202218794

  日期：2023.3.20

  We report an iridium-catalyzed highly chemo-, diastereo-, and enantioselective allyl-allyl coupling between branched allyl alcohols and α-silyl-substituted allylboronate esters resulting in enantioenriched (E)-1-boryl-substituted 1,5-dienes. All four stereoisomers with two adjacent chiral centers were obtained by chirality pairing. Mechanistic studies were conducted to understand the high levels of

  我们报告了支链烯丙醇和 α-甲硅烷基取代的烯丙基硼酸酯之间的铱催化的高度化学、非对映和对映选择性烯丙基-烯丙基偶联，导致对映体富集 (E)-1-硼基取代的 1,5-二烯。所有四种具有两个相邻手性中心的立体异构体都是通过手性配对获得的。进行了机理研究以了解高水平的选择性。
• Synthesis of Optically Active Boron–Silicon Bifunctional Cyclopropane Derivatives through Enantioselective Copper(I)‐Catalyzed Reaction of Allylic Carbonates with a Diboron Derivative
  作者：Hajime Ito、Yuki Kosaka、Kousuke Nonoyama、Yusuke Sasaki、Masaya Sawamura

  DOI：10.1002/anie.200802342

  日期：2008.9.15
• 1-Silyl-1-boryl-2-alkenes: Reagents for Stereodivergent Allylation Leading to 4-Oxy-(E)-1-alkenylboronates and 4-Oxy-(Z)-1-alkenylsilanes
  作者：Masaki Shimizu、Hirotaka Kitagawa、Takuya Kurahashi、Tamejiro Hiyama

  DOI：10.1002/1521-3773(20011119)40:22<4283::aid-anie4283>3.0.co;2-3

  日期：2001.11.19

  Silylboryl reagents for organic synthesis: 1-silyl-1-boryl-2-alkenes (2) were prepared efficiently by gem-silylborylation of α-chloroallyllithium compounds from (dimethylphenylsilyl)(pinacolato)borane (1; see scheme, LDA=lithium diisopropylamide) and were demonstrated to allylate acetals and aldehydes in the presence of a Lewis acid to produce (E)-4-alkoxy-alkenylboronates. Heating the reagents with aldehydes in the absence of Lewis acid afforded (Z)-4-hydroxy-alkenylsilanes stereospecifically.