2-(2,4-pentadienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 438497-80-4

• 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-(2,4-pentadienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-(2,4-Pentadienyl)-4,4,5,5-tetramethyl-1,3.2-dioxaborolane；4,4,5,5-tetramethyl-2-penta-2,4-dienyl-1,3,2-dioxaborolane
• CAS: 438497-80-4
• 化学式: C₁₁H₁₉BO₂
• 分子量: 194.082
• InChiKey: STZAADOLJDRMBP-UHFFFAOYSA-N

物化性质

• 沸点：
  222.4±19.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.82
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 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-(2,4-pentadienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 4,5-双二苯基膦-9,9-二甲基氧杂蒽 、 copper(l) chloride 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 3.75h， 生成 rac-(E)-tert-butyldimethyl((1-phenylhexa-3,5-dien-1-yl)oxy)silane
  参考文献：
  名称：

  (E)-δ-乙烯基-高烯丙醇的铜催化高立体选择性合成

  摘要：

  开发了 ( E )-δ-乙烯基-高烯丙醇的立体选择性合成。从 α-乙烯基烯丙基硼酸酯开始，Cu 催化的醛或酮烯丙基化形成具有高E选择性的仲或叔 δ-乙烯基高烯丙醇。提出该反应在 Curtin-Hammett 原理下通过 α-乙烯基烯丙基铜物种的中介进行，以产生具有高E选择性的醇产物。

  DOI：

  10.1021/acs.orglett.1c02086
• 作为产物：
  描述：

  potassium pentadienide 以 四氢呋喃 为溶剂， 生成 2-(2,4-pentadienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Borabenzene derivatives. 21. 2,4-Pentadienylboranes as key intermediates of a novel route to boracyclohexadienes and boratabenzenes. Structure of [Li(TMPDA)](C5H5BNMe2)

  摘要：

  Under metalation conditions the 2,4-pentadienylboranes 2,4-C5H7B(NR2)2 (R = Me, Et) and 2,4-C5H7B(O2C2Me4) undergo an electrocyclic ring closure to form borabenzene derivatives. This novel reaction provides a far more efficient access to borabenzene chemistry than previous methods. The dimethylamino derivative [Li{Me2N(CH2)3NMe2}](C5H5BNMe2) is the first boratabenzene salt to be structurally characterized.

  DOI：

  10.1021/om00032a008

文献信息

• Method for preparation of boratabenzene derivatives
  申请人：Equistar Chemicals, L.P.

  公开号：US06410764B1

  公开（公告）日：2002-06-25

  A process for preparing boratabenzene derivatives is provided. The process includes the hydrogenation of a compound containing a boranaphthalene functional group to form a boratabenzene-containing compound. Depending on the compound containing a boranaphthalene functional group, the resulting boratabenzene compound may be converted into a catalyst suitable for olefin polymerization. A process for forming a boratabenzene derivative from a halo-dioxaborolane is also provided. In this process, a halo-dioxaborolane is reacted with a piperylide salt for form a pentadienyl dioxaborolane. The pentadienyl-dioxaborolane is reacted with a strong base to form an intermediate boratacyclohexanediene salt. The intermediate boratacyclohexanediene salt is then reacted with a trialkylaluminum compound to form an alkylboratabenzene salt.

  本发明提供了制备硼代苯衍生物的方法。该方法包括将含有硼萘基团的化合物加氢，形成含有硼代苯基团的化合物。根据含有硼萘基团的化合物不同，所得的硼代苯化合物可以转化为适用于烯烃聚合的催化剂。本发明还提供了一种从卤代二氧硼烷形成硼代苯衍生物的方法。在该方法中，将卤代二氧硼烷与吡啶盐反应，形成戊二烯基二氧硼烷。戊二烯基二氧硼烷与强碱反应，形成中间体硼代环己二烯基盐。然后将中间体硼代环己二烯基盐与三烷基铝化合物反应，形成烷基硼代苯盐。
• Hoffmann, Reinhard W.; Landmann, Bernd, Chemische Berichte, 1986, vol. 119, # 3, p. 1039 - 1053
  作者：Hoffmann, Reinhard W.、Landmann, Bernd

  DOI：——

  日期：——
• Borabenzene Derivatives. 22. Synthesis of Boratabenzene Salts from 2,4-Pentadienylboranes. Structure of [NMe3Ph][C5H5BMe]
  作者：Gerhard E. Herberich、Bernd Schmidt、Ulli Englert

  DOI：10.1021/om00001a064

  日期：1995.1

  Borylation of potassium pentadienide with BCl(NR(2))(2) and subsequent alcoholysis produce 2,4-pentadienylboranes C5H7B(NR(2))(2) (4a-c: R = Me, Et, Pr-i), C5H7B(OR)(2) (4e,f: R = Et, Bu(t)), and C5H7B(OCR(2))(2) with 1,3,2-dioxaborolane rings (4g,h: R = H, Me) as mixtures of E and Z isomers. Metalation of 4a,b in THF by lithium dialkylamides LiNR'(2) (R' = Me, Et, Pr-i) in the presence of TMEDA. results fi) in a nonproductive deborylation via primary attack at the boron center, (ii) in ring closure to produce boratabenzene salts [Li(TMEDA)][C5H5-BNR(2)] (10a,b: R = Me, Et), and (iii) in substitution of B-dialkylamino groups when NR(2) is bulkier than NR'(2). 10a is obtained in 26.5% yield. Metalation of 4h in THF by the sterically demanding lithium dialkylamides LDA and LiTMP affords a precipitate of the spiroborate [Li(THF][C5H6B(OCMe(2))(2)] (13) in 63% yield in equilibrium with the presumed isomer Li-[C5H5BO(CMe(2))(2)OH] (Li(Sg)) in the THF solution. 13 can be transformed into boratabenzenes by several methods. (i) Treatment with Me(3)SiCl produces a 1:1 mixture of isomeric boracyclohexadienes C(5)H(6)BOCMe(2)CMe(2)OSiMe(3) (15a, 2,4-isomer; 15b, 2,5-isomer) which, on subsequent low-temperature metalation, give Li[C5H5BO(CMe(2))OSiMe(3)] (Li(3h)). (ii) Metalation of 13 at -78 degrees C affords Li-2[C5H5BO(CMe(2))O] (Li-2(3i)) and, after treatment with Me(3)SiCl, the bora-2,4-cyclohexadiene (5-Me(3)Si)C(5)H(5)BOCMe(2)CMe(2)OSiMe(3) (16). (iii) Treatment of 13 with Al(2)Me(6) in toluene at -78 degrees C affords Li[C(5)H(5)BMe] (Li(3b)) in 79% yield as a white solid. This salt is also obtained from Li(3h) and Al(2)Me(6). (iv) Addition of 15 to LiBu(t) in pentane/hexane produces Li[C(5)H(5)BBu(t)] (Li(3c)) in 53% yield. Combining strongly alkaline aqueous solutions of[NMe(3)Ph]I and Li(3b) affords [NMe(3)Ph][C(5)H(5)BMe] (18). 18 crystallizes in the monoclinic space group P2(1)/n with a = 935.4(1) pm, b = 1557.4(4) pm, c = 988.8(1) pm, beta = 95.47(1)degrees, and Z = 4. The 1-methylboratabenzene ion of 18 displays nearly perfect C-2 nu symmetry with intra-ring bond distances of 150.1, 138.8, and 139.2 pm (average) for B-C1 (B-C5), C1-C2 (C4-C5), and C2-C3 (C3-C4), respectively.
• Borabenzene derivatives. 21. 2,4-Pentadienylboranes as key intermediates of a novel route to boracyclohexadienes and boratabenzenes. Structure of [Li(TMPDA)](C5H5BNMe2)
  作者：Gerhard E. Herberich、Bernd Schmidt、Ulli Englert、Trixie Wagner

  DOI：10.1021/om00032a008

  日期：1993.8

  Under metalation conditions the 2,4-pentadienylboranes 2,4-C5H7B(NR2)2 (R = Me, Et) and 2,4-C5H7B(O2C2Me4) undergo an electrocyclic ring closure to form borabenzene derivatives. This novel reaction provides a far more efficient access to borabenzene chemistry than previous methods. The dimethylamino derivative [LiMe2N(CH2)3NMe2}](C5H5BNMe2) is the first boratabenzene salt to be structurally characterized.
• Cu-Catalyzed Highly Stereoselective Syntheses of (<i>E</i>)-δ-Vinyl-homoallylic Alcohols
  作者：Jiaming Liu、Bo Su、Ming Chen

  DOI：10.1021/acs.orglett.1c02086

  日期：2021.8.6

  developed. Starting from α-vinyl allylboronate, Cu-catalyzed allylation of aldehydes or ketones forms secondary or tertiary δ-vinyl-homoallylic alcohols with high E-selectivities. It is proposed that the reaction operates under the Curtin–Hammett principle via the intermediacy of α-vinyl allylic copper species to give the alcohol products with high E-selectivities.

  开发了 ( E )-δ-乙烯基-高烯丙醇的立体选择性合成。从 α-乙烯基烯丙基硼酸酯开始，Cu 催化的醛或酮烯丙基化形成具有高E选择性的仲或叔 δ-乙烯基高烯丙醇。提出该反应在 Curtin-Hammett 原理下通过 α-乙烯基烯丙基铜物种的中介进行，以产生具有高E选择性的醇产物。