(E,E)-(5-hydroxy-3-methylpenta-1,3-dienyl)boronic acid | 120040-83-7

• 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: (E,E)-(5-hydroxy-3-methylpenta-1,3-dienyl)boronic acid
• 英文别名: [(1E,3E)-5-hydroxy-3-methylpenta-1,3-dienyl]boronic acid
• CAS: 120040-83-7
• 化学式: C₆H₁₁BO₃
• 分子量: 141.963
• InChiKey: SSKZPAXOAVZWCQ-PIXFVPMGSA-N

物化性质

• 沸点：
  335.0±44.0 °C(Predicted)
• 密度：
  1.099±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.51
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  60.7
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E,E)-(5-hydroxy-3-methylpenta-1,3-dienyl)boronic acid 在 manganese(IV) oxide 、 四(三苯基膦)钯 、 正丁基锂 、 氢氧化铊(Ⅰ) 、 四丁基氟化铵 、 水 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 (2E,4E,6E,8E)-3,6-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)nona-2,4,6,8-tetraenal
  参考文献：
  名称：

  Experimental and Theoretical Analysis of the Steric Tolerance of the Binding Site of Bacterioopsin with the Use of Side-Chain Methyl-Shifted Retinal Analogs

  摘要：

  Four positional isomers of trans-retinal (1) differing in the location of the side-chain methyl groups have been prepared by a combination of Wittig and highly stereocontrolled Suzuki coupling reactions. The incubation of 9-demethyl-10-methylretinal (5) with bacterioopsin yielded an artificial pigment with an opsin shift of 4630 cm(-1) The other three analogs, namely 13-demethyl-14-methylretinal (3), 13-demethyl-12-methylretinal (4), and 9-demethyl-8-methylretinal (6) did not bind to the apoprotein. In order to rationally address the intrinsic structural differences among analogs which could be relevant to the discrimination exhibited by the protein binding site, ab initio calculations with complete optimization at the 3-21G level were performed on model N-methylretinal iminium salts derived from aldehydes 1 and 3-6. The validity of the approach was inferred from the remarkable coincidence between the minimized structure of N-methylretinal Schiff base (PSB-1) and the structural parameters displayed by N-methyl-N-phenylretinal iminium perchlorate (38b). Computations clearly show that the location of the methyl groups on the polyene side chain is of the utmost importance in determining the overall shape of the retinal ligands. Those structural effects, added to the dominant steric and electronic restrictions of the binding pocket, would explain the observed discrimination among the analogs 3-6, with minor structural changes, and perhaps among other retinals reported in the literature. Additionally, the theoretical and experimental results obtained with 9-demethyl-8-methylretinal (6) provide further indirect evidence of the importance of the 6-s-trans conformation for the native chromophore in bacteriorhodopsin.

  DOI：

  10.1021/ja00136a021
• 作为产物：
  描述：

  (Z)-3-bromobut-2-en-1-ol 以75%的产率得到
  参考文献：
  名称：

  ROUSH, WILLIAM R.;BROWN, BRADLEY B.;DROZDA, SUSAN E., TETRAHEDRON LETT., 29,(1988) N 29, C. 3541-3544

  摘要：

  DOI：

文献信息

• Synthesis of 2,4-Dibromopyridine and 4,4’-Dibromo-2,2’-bipyridine. Efficient Usage in Selective Bromine-Substitution under Palladium-Catalysis
  作者：Mar誕-Magdalena Cid、Ram溶 Garc誕-Lago、Jos�-Lorenzo Alonso-G洋ez、Cristina Sicre

  DOI：10.3987/com-07-11170

  日期：——

  4’-dihalo-2,2’-bipyridines from dihalopyridines via a Stille reaction is also described. 4,4'-Dibromo-2,2’-bipyridine undergoes selective monoor disubstitution processes under palladium catalysis. This short synthetic procedure is an efficient and reliable process for preparing conjugated pyridine and 2,2’-bipyridine building blocks for applications in coordination chemistry and materials science. INTRODUCTION

  −我们报道了一种通过串联亲核取代-N-氧化物还原过程一步一步从相应的硝基嗪N-氧化物制备2,4-二溴吡啶和4,4'-二溴-2,2'-联吡啶的有效方法。还描述了通过 Stille 反应从二卤代吡啶一步制备 4,4'-二卤代-2,2'-联吡啶。4,4'-二溴-2,2'-联吡啶在钯催化下发生选择性单取代或双取代过程。这种简短的合成过程是制备用于配位化学和材料科学的共轭吡啶和 2,2'-联吡啶结构单元的有效且可靠的方法。引言 为开发吖嗪类化合物，特别是吡啶类和 2,2'-联吡啶类的合成方法，人们付出了广泛的努力，由于它们在许多天然产物和药物中作为亚结构存在，也作为过渡金属的配体存在。在很大程度上，由于它们能够充当几乎所有种类的金属离子的螯合剂，以及由于它们在超分子化学和材料科学中的参与而产生的广泛应用，这在很大程度上推动了人们对这种化学的重新兴趣。然而，合成获得功能化衍生物仍然很困难，因此非常需要
• Application of the steric directing group strategy to the stereoselective synthesis of the octahydronaphthalene substructure of kijanolide and tetronolide
  作者：William R. Roush、Bradley B. Brown

  DOI：10.1021/ja00059a024

  日期：1993.3

  A highly selective synthesis of the kijanolide/tetronolide octahydronaphthalene substructure 4 has been completed. The synthesis proceeds in 16 steps from L-glyceraldehyde acetonide (8), with 88% stereoselectivity and in 11% overall yield. Key steps are the following: (1) the asymmetric crotylborations or 8 and 12 that introduce the C(5), C(6), and C(8) stereocenters or 4; (2) the modified Suzuki coupling

  kijanolide/tetronolide八氢化萘亚结构4的高选择性合成已经完成。该合成从 L-甘油醛丙酮化物 (8) 分 16 个步骤进行，立体选择性为 88%，总产率为 11%。关键步骤如下： (1) 引入 C(5)、C(6) 和 C(8) 立体中心或 4 的不对称 crotyborations 或 8 和 12；(2) 改性 Suzuki 偶联或乙烯基硼酸 36 和二溴烯烃 31，在单个操作中建立共轭三烯单元并引入 C(9) Br 空间导向基团；(3) 四烯 7 的高立体选择性分子内 Diels-Alder 环加成反应
• A highly stereoselective synthesis of the octahydronaphthalene subunit of kijanolide and tetronolide
  作者：William R. Roush、Bradley B. Brown、Susan E. Drozda

  DOI：10.1016/0040-4039(88)85287-0

  日期：1988.1

  A highly stereoselective synthesis of the octahydronaphthalene subunit 4 of kijanolide and tetronolide featuring the intramolecular Diels-Alder reaction of tetraenoate 5 is described.

  描述了具有四烯酸酯5的分子内Diels-Alder反应的特征的环烷醇和四氢萘酚的八氢萘亚基4的高度立体选择性合成。
• Studies on the synthesis of kijanolide: synthesis of the 2-acyl spirotetronate and investigations concerning the coupling of the top and bottom half fragments
  作者：William R. Roush、Bradley B. Brown

  DOI：10.1021/jo00060a036

  日期：1993.4

  Several studies directed toward the synthesis of kijanolide are described. First, a method for synthesis of the 2-acyl spiro tetronate substructure (15,52) via a Dieckmann cyclization protocol was developed. Second, a 10-step synthesis of 7,7-dibromo-2,4-dimethyl-5-[(tert-butyldiphenylsilyl)oxy]heptenal 35 was developed, making possible the synthesis of a range of kijanolide bottom half precursors via olefination (e.g., 35 + 23 --> 38) and cross-coupling reactions (e.g., 38 --> 19). This solves the problems encountered due to the introduction of the C(7)-hydroxyl group in our previous synthesis of the kijanolide bottom half 2.2a Third, a highly efficient procedure was developed for the coupling of kijanolide top half 8 and dioxinone 38 via an acyl ketene intermediate. This is the most efficient of several methods examined for acylating the hindered tertiary hydroxyl group of 8. Attempts to perform the IMDA reaction of 46, 47 or 9 (R = SiEt3) generated in situ from coupling of 8 and the acyl ketene (20) derived from 42 were thwarted by the unexpected tendency of beta-keto esters like 47 to fragment and decarboxylate via the acyl ketene intermediate at temperatures above 115-degrees-C. 2-Acyl tetronates 53 and 54 were prepared, but these systems decomposed upon attempted IMDA cyclization at temperatures approaching 190-degrees-C.
• A Formal Total Synthesis of (+)-Tetronolide, the Aglycon of the Tetrocarcins:  Enantio- and Diastereoselective Syntheses of the Octahydronaphthalene (Bottom-Half) and Spirotetronate (Top-Half) Fragments
  作者：William R. Roush、Melissa L. Reilly、Kazuo Koyama、Bradley B. Brown

  DOI：10.1021/jo970960c

  日期：1997.12.1

  A formal total synthesis of (+)-tetronolide, the aglycon of the tetrocarcins, has been achieved by virtue of the development of highly diastereo-and enantioselective syntheses of the bottom- and top-half fragments 4 and 5 reported herein. These fragments previously served as key intermediates in Yoshii's pioneering total synthesis of (+)-tetronolide, The synthesis of the bottom-half octahydronaphthalene unit 4 features the intramolecular Diels-Alder reaction of tetraenal 20 and proceeds in 17 steps and 5-6% yield from D-glyceraldehyde pentylidene acetal 8. The synthesis of the spirotetronate fragment 5 features the highly enantioselective exo selective Diels-Alder reaction of triene 37 and chiral dienophile 25b and proceeds in 14 steps and 10% overall yield from cis-2-butene-1,4-diol (38). An enantioselective synthesis of Boeckman's top-half cyclohexene fragment 6 sia the exo selective Diels-Alder reaction of diene 24 and dienophile 25a was also developed, but this route was deemed too inefficient for use in a projected total synthesis of the natural product. The syntheses of 5 and 6 provide important information on the utility of chiral dienophiles 25a and 25b in organic synthesis.