1,2-(bis)pinacolatoborolanyl-1-phenyl-1-butene | 179117-39-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,2-(bis)pinacolatoborolanyl-1-phenyl-1-butene
• 英文别名: (Z)-2,2'-(1-phenylbut-1-ene-1,2-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)；4,4,5,5-Tetramethyl-2-[(Z)-1-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-butenyl]-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-[(Z)-1-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-1-en-2-yl]-1,3,2-dioxaborolane
• CAS: 179117-39-6
• 化学式: C₂₂H₃₄B₂O₄
• 分子量: 384.132
• InChiKey: HVIBQNOZQBVVDT-ZCXUNETKSA-N

物化性质

• 沸点：
  390.7±52.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-(bis)pinacolatoborolanyl-1-phenyl-1-butene 在 二氟化氢钾 、 tetra-N-butylammonium tribromide 作用下， 以 甲醇 、 水 、 四氢呋喃 为溶剂， 反应 0.5h， 生成 (Z)-1,2-Dibromo-1-phenylbutene
  参考文献：
  名称：

  使用三溴化四丁基铵或三碘化铯对有机三氟硼酸盐进行卤代硼烷化

  摘要：

  报道了在水介质中使用市售的三溴化四丁基铵（TBATB）或三碘化铯对有机三氟硼酸盐进行卤代硼烷化。事实证明，这种温和的不含过渡金属的方法可耐受多种官能团。观察到高的区域选择性和化学选择性。两个合成路线（ż）从炔-dibromoalkenes，通过stereodefined（ż）-2- bromoalkenyltrifluoroborates和（Ž）-1,2-双（硼烷基）alkenyltrifluoroborates，已经使用TBATB介导bromodeboronation作为关键步骤开发的。

  DOI：

  10.1016/j.tet.2012.03.016
• 作为产物：
  描述：

  1-苯基-1-丁炔 、 联硼酸频那醇酯 在 四(三苯基膦)铂 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.02h， 生成 1,2-(bis)pinacolatoborolanyl-1-phenyl-1-butene
  参考文献：
  名称：

  微波辅助一锅法去孔/铃木交叉耦合。快速获得四取代烯烃的途径

  摘要：

  内部和末端炔烃在二恶烷中用双（频哪醇）二硼进行铂（0）催化的快速硼氢化反应，在密封容器微波条件下生成顺式-1,2-双（硼基）烯烃。随后将芳基溴化物，碱和钯催化剂加至反应瓶中，然后再置于微波条件下，通过硼中间体的铃木（Suzuki）交叉偶联以高收率提供四取代的乙烯。

  DOI：

  10.1016/j.tetlet.2008.06.017

文献信息

• Copper-Catalyzed Borylation Reactions of Alkynes and Arynes
  作者：Hiroto Yoshida、Shota Kawashima、Yuki Takemoto、Kengo Okada、Joji Ohshita、Ken Takaki

  DOI：10.1002/anie.201106706

  日期：2012.1.2

  One, two, three, four: A copper(I)–phosphine complex catalyzes the diborylation of alkynes and arynes, and the tri‐ or tetraborylation of propargyl ethers (see scheme; pin=pinacolato). In the latter cases, the CO bond(s) as well as the CC bond are borylated in one pot. Furthermore, a diborylation product serves as an intermediate in the efficient synthesis of ortho‐terphenyls with pharmacological

  一，二，三，四：铜（I）-膦配合物催化炔烃和芳烃的二硼化，以及炔丙基醚的三硼化或四硼化（参见方案； pin = pinacolato）。在后一种情况下，将C  O键（一个或多个）以及所述CC键被borylated一锅。此外，二氢甲酰化产物是有效合成具有药理活性的邻三联苯的中间体。
• Palladium-catalyzed double cross-coupling reaction of 1,2-bis(pinacolatoboryl)alkenes and -arenes with 2,2′-dibromobiaryls: annulative approach to functionalized polycyclic aromatic hydrocarbons
  作者：Masaki Shimizu、Ikuhiro Nagao、Yosuke Tomioka、Tsugumi Kadowaki、Tamejiro Hiyama

  DOI：10.1016/j.tet.2011.08.019

  日期：2011.10

  This study demonstrates that the double cross-coupling reaction of 1,2-bis(pinacolatoboryl)alkenes and -arenes with 2,2′-dibromobiaryls proceeds smoothly with the aid of a catalytic amount of Pd(PPh3)4 in the presence of excess base to give a variety of polycyclic aromatic hydrocarbons, such as phenanthrenes, [5]helicene, dithienobenzenes, triphenylenes, dibenzo[g,p]chrysenes, and triphenyleno[1,2-b:4

  这项研究表明，在催化量的Pd（PPh 3）4存在下，1,2-双（频哪醇硼基）烯烃和-芳烃与2,2'-二溴联芳基的双交叉偶联反应可以顺利进行。过量的碱可得到各种多环芳烃，例如菲，[5]螺旋烯，二硫代苯，三苯撑，二苯并[ g，p ]，和三苯并[1,2- b：4,3- b ']二噻吩好到高产。值得注意的是，使用2,2'-二溴八氟联苯作为亲电试剂的环化反应提供了否则难以合成的八氟菲和半氟化二苯并[ g，p] chrysenes高产。
• Dehydrogenative Diboration of Alkynes Catalyzed by Ir/CO/tBuNC System
  作者：Qingheng Lai、Oleg V. Ozerov

  DOI：10.1016/j.jorganchem.2020.121614

  日期：2021.1

  dehydrogenative diboration (DHDB) of alkyne with HBpin was achieved using [Ir(COD)Cl]2 and other related Ir precursors under CO atmosphere. The selectivity for DHDB over hydroboration was higher in less polar solvents and under higher CO pressure. It was further improved when catalytic amount of tBuNC was added to the reaction. It was possible to achieve DHDB of both terminal and internal alkynes with selectivity

  在CO气氛下，使用[Ir（COD）Cl] 2和其他相关的Ir前体，实现了HBpin炔烃的催化脱氢硼氢化（DHDB）。在极性较小的溶剂中和较高的CO压力下，DHDB在硼氢化反应中的选择性较高。当将催化量的t BuNC加入反应中时，其进一步改善。在最佳条件下，对末端和内部炔烃的DHDB选择性可达9：1。某些DHDB产品已按制备规模分离。
• Microwave-assisted one-pot diboration/Suzuki cross-couplings. A rapid route to tetrasubstituted alkenes
  作者：Hana Prokopcová、Jesús Ramírez、Elena Fernández、C. Oliver Kappe

  DOI：10.1016/j.tetlet.2008.06.017

  日期：2008.8

  terminal alkynes undergo rapid platinum(0)-catalyzed diboration with bis(pinacolato)diboron in dioxane to yield cis-1,2-bis(boryl)alkenes under sealed vessel microwave conditions. Subsequent addition of aryl bromides, base and a palladium catalyst to the reaction vial followed by resubjection to microwave conditions provides tetrasubstituted ethylenes in high yields via Suzuki cross-coupling of the boron

  内部和末端炔烃在二恶烷中用双（频哪醇）二硼进行铂（0）催化的快速硼氢化反应，在密封容器微波条件下生成顺式-1,2-双（硼基）烯烃。随后将芳基溴化物，碱和钯催化剂加至反应瓶中，然后再置于微波条件下，通过硼中间体的铃木（Suzuki）交叉偶联以高收率提供四取代的乙烯。
• N-Alkoxypyrazoles as biomimetics for the alkoxyphenyl group in tamoxifen
  作者：Martin Wenckens、Palle Jakobsen、Per Vedsø、Per Olaf Huusfeldt、Birgitte Gissel、Marianne Barfoed、Bettina Lundin Brockdorff、Anne E Lykkesfeldt、Mikael Begtrup

  DOI：10.1016/s0968-0896(02)00566-7

  日期：2003.4

  The preparation of a series of novel analogues of the selective antiestrogen tamoxifen is reported. 1Z-alkoxyphenyl group in tamoxifen has been replaced by a N-alkoxypyrazole, while functionalised phenyl groups or heteroaromatics were introduced at the 2Z-position using sequential Suzuki cross coupling of 1,2-(bis)borylpinacol 1-phenylbutene with 4- or 5-iodo-1-N,N-dimethylaminoethyl or propyl-pyrazoles. Approximately 50 tamoxifen analogues were obtained and tested in an estrogen receptor (ERalpha) affinity assay. Several compounds exhibited binding affinities 2-5-fold lower than tamoxifen. Dose-response experiments with six selected compounds were carried out using two different human breast cancer cell lines, MCF-7 and the tamoxifen resistant cell line MCF-/TAM(R)-1. Both cell lines exhibited growth inhibition upon treatment with the tamoxifen analogues. Co-treatment of the cells, with estradiol and the individual compounds, were also performed. The results indicated that the observed growth inhibitory effect was mediated by the ERalpha. Analogues of the potent antiestrogen 4-hydroxytamoxifen (4-OHT) were synthesised where the 1E-4-hydroxyphenyl was replaced by a 1-hydroxypyrazol-4-yl group. However, modest growth inhibition of MCF-7 cells was observed upon treatment with these analogues. In contrast, 1Z-, 2Z-ringclosed tamoxifen analogue (59) was shown to possess antiproliferative effects on MCF-7 and MCF-/TAM(R)-1 cells in lower doses than tamoxifen. (C) 2003 Elsevier Science Ltd. All rights reserved.