[(1E)-6-羟基-1-己烯-1-基]硼酸 | 132047-94-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 中文名称: [(1E)-6-羟基-1-己烯-1-基]硼酸
• 英文名称: (E)-6-hydroxyhex-1-en-ylboronic acid
• 英文别名: (E)-6-hydroxyhex-1-enylboronic acid；(6-hydroxy-1-hexenyl)boronic acid；(E)-6-Hydroxy-1-hexenylboronic acid；[(E)-6-hydroxyhex-1-enyl]boronic acid
• CAS: 132047-94-0
• 化学式: C₆H₁₃BO₃
• 分子量: 143.978
• InChiKey: FQAFREIIXSZWOK-HWKANZROSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.28
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  [(1E)-6-羟基-1-己烯-1-基]硼酸 在 四丙基高钌酸铵 N-甲基吲哚酮 、 potassium hydrogen bifluoride 、 4 A molecular sieve 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.33h， 生成 tetra-n-butylammonium (E)-5-formylpent-1-enyltrifluoroborate
  参考文献：
  名称：

  Oxidation of Hydroxyl-Substituted Organotrifluoroborates

  摘要：

  Potassium- and tetra-n-butylammonium organotrifluoroborates containing hydroxyl groups have been prepared and oxidized using several common oxidants. Aryl-, alkenyl-, and alkyltrifluoroborates containing both primary and secondary hydroxyl groups were oxidized in moderate to excellent yields with complete retention of the trifluoroborate moiety. The utility of these oxidized products was demonstrated in a Suzuki-Miyaura cross-coupling reaction.

  DOI：

  10.1021/ja062974i
• 作为产物：
  描述：

  5-己炔-1-醇 在 儿萘酚硼烷 、 水 作用下， 反应 23.0h， 以51%的产率得到[(1E)-6-羟基-1-己烯-1-基]硼酸
  参考文献：
  名称：

  Oxidation of Hydroxyl-Substituted Organotrifluoroborates

  摘要：

  Potassium- and tetra-n-butylammonium organotrifluoroborates containing hydroxyl groups have been prepared and oxidized using several common oxidants. Aryl-, alkenyl-, and alkyltrifluoroborates containing both primary and secondary hydroxyl groups were oxidized in moderate to excellent yields with complete retention of the trifluoroborate moiety. The utility of these oxidized products was demonstrated in a Suzuki-Miyaura cross-coupling reaction.

  DOI：

  10.1021/ja062974i

文献信息

• Regioselective palladium-catalyzed cross-coupling reactions in the synthesis of novel 2,3-disubstituted thiophene derivatives
  作者：Raquel Pereira、Beatriz Iglesias、Angel R de Lera

  DOI：10.1016/s0040-4020(01)00764-5

  日期：2001.9

  A reactivity optimization study of the palladium-catalyzed cross-coupling reactions of 2,3-dibromothiophene and organometallic reagents has been conducted. Regioselective coupling at the C2 position, accomplished most notably by Suzuki coupling, was combined with a Stille reaction at C3 using Fu's modification, to afford the 2,3-disubstituted thiophene derivatives.

  进行了钯，2,3-二溴噻吩与有机金属试剂的交叉偶联反应的反应性优化研究。C2位置的区域选择性偶联（最明显地是通过Suzuki偶联完成的）与Fu修饰在C3的Stille反应结合，得到2,3-二取代的噻吩衍生物。
• Keynote article. Nickel catalysed coupling of allylamines and boronic acids
  作者：Barry M. Trost、Michel D. Spagnol

  DOI：10.1039/p19950002083

  日期：——

  vinyl derivatives, E-isomers couple more efficiently than Z-isomers and both fully retain the geometrical integrity. Methylations preferably employ the boronic esters like 2-methyl-1,3,2-benzodioxaborole or 2-methyl-1,3,2-dioxaborolane rather than methylboronic acid. The stereochemistry of the reaction involves a net inversion with respect to the allylamine. The regioselectivity is a function of ligand

  烯丙胺在镍（0）催化剂而不是钯（0）催化剂存在下作为与硼酸交叉偶联的底物。芳基，乙烯基和甲基硼酸的作用良好。使用乙烯基衍生物，E异构体比Z偶联更有效-异构体和两者完全保留几何完整性。甲基化优选使用硼酸酯，例如2-甲基-1,3,2-苯并二恶唑硼酸酯或2-甲基-1,3,2-二氧杂硼烷，而不是甲基硼酸。反应的立体化学涉及烯丙基胺的净转化。区域选择性是配体的函数。通常，空间大的供体膦在取代度较低的位置促进新的C–C键形成。双齿配体，特别是1,1'-联萘-2,2'-双（二苯基次膦基）（BINAPO），可在取代度更高的烯丙基末端促进新的C–C键形成。与烯丙醇和与硼酸形成的酯相比，胺似乎是优选的伴侣，并具有更高的立体特异性。
• Enantioselective synthesis of the bottom half of chlorothricolide. 3. Studies of the steric directing group strategy for stereocontrol in intramolecular Diels-Alder reactions
  作者：William R. Roush、Masanori Kageyama、Renata Riva、Bradley B. Brown、Joseph S. Warmus、Kevin J. Moriarty

  DOI：10.1021/jo00003a049

  日期：1991.2

  The intramolecular Diels-Alder reactions of a series of C(7)-alkoxy-substituted 2(E),8(Z),10(E)-undecatrienoates and trienals containing removable C(9)-Br or C(9)-SiMe3 substituents (11, 12, 13, 33, 42, 43, 44, 45) were studied as part of a program directed toward the total synthesis of the bottom half of chlorothricolide. The IMDA reaction of trienoate 3 that lacks a C(9) substituent had previously been shown to cyclize with poor stereoselectivity to a mixture of four cycloadducts. It was expected that the IMDA reactions of trienes containing C(9) substituents (i.e., steric directing groups) would proceed with substantially enhanced stereoselectivity via trans-fused transition state A owing to nonbonded interactions that the steric directing groups experience in the competitive transition states B-D. Cis-fused transition states C and D suffer from serious interactions between C(9)-X and the axial C(6)-H, while trans-fused transition state B is destabilized by a 1,3-eclipsing interaction with the C(7)-alkoxyl group. Only the desired transition state, trans-fused transition state A, suffers from no serious interactions involving the C(9) steric directing group. These predictions were verified experimentally: the trans-fused cycloadduct deriving from A was the major product in all cases. Stereoselectivity for trans-fused cycloadducts was consistently greater, using C(9)-TMS directing groups compared to C(9)-Br substituted systems (for IMDA reactions under analogous conditions), but the C(9)-Br group appeared to have a greater influence on the partition between transition states A and B (see Table I). A surprising aspect of this study, however, is that significant amounts of cis-fused cycloadducts were obtained from the thermal cyclizations of the above-named trienes (12-45%), and this pathway was not entirely suppressed even in the Lewis acid catalyzed cycloadditions of trienals 44 and 45 (5-9% of cis fused cycloadduct). The results with TMS-substituted trienes 33, 42, and 44 thus are in disagreement with an earlier report by Boeckman and Barta (ref 5f) that the IMDA reaction of 33 gives ''a single cycloadduct (> 100:1).'' The cis-fused diastereomers most probably arise via boat-like transition state E rather than the chair-like transition state C. Cis-fused cycloadducts were not observed in the IMDA reaction of TMS-substituted triene 61 that lacks a C(7)-alkoxy substituent, suggesting that the C(7)-alkoxy groups electronically deactivate trans-fused transition state A such that boat-like transition state E is competitive only with substrates containing such C(7)-alkoxy substituents. Data are also presented that show that the C(9)-TMS substituents lead to an increase in reactivity (e.g., the IMDA reaction of 61 that proceeds at ambient temperature and the acid-catalyzed cyclocondensation of TMS diene aldehyde 63). This study defines bromo trienoate 43 as the optimal precursor to the bottom half unit (2) of chlorothricolide, even though the IMDA reaction of 43 is less selective than that of TMS-substituted trienes 42 and 44. The synthesis of 43 (Figure 4) involving the Pd0-catalyzed cross-coupling reaction of dibromo olefin 35 and vinylboronate 37 is shorter and considerably more efficient than the syntheses of TMS trienes 42 and 44, and this compensates for the fact that 43 is the least selective IMDA substrate.Syntheses that proceed by way of TMS trienoates like 42 or TMS trienals like 44 become competitive only if a more efficient triene synthesis is devised.
• Regioselectivity in alkenyl(aryl)-heteroaryl Suzuki cross-coupling reactions of 2,4-dibromopyridine. A synthetic and mechanistic study
  作者：Cristina Sicre、J.-Lorenzo Alonso-Gómez、M. Magdalena Cid

  DOI：10.1016/j.tet.2006.09.040

  日期：2006.11

  2,4-Dibromopyridine undergoes a regioselective Suzuki cross-coupling reaction at position 2 with several alkenyl(aryl) boronic acids to render 4-bromo-2-carbon substituted pyridines, difficult to be prepared otherwise, in good yields under palladium catalysis, either Pd(PPh3)(4)/TlOH or Pd(2)dba(3)/PCy3/K3PO4 at 25 degrees C. This behavior is explained on the basis of the electrophilic character of both C-Br bonds, being their relative reactivity in 2,4-dibromopyridine similar to that in the corresponding monobromopyridines. In addition, the dicoupled compound 6 is not formed through a double oxidative addition of 2,4-dibromopyri dine to Pd(PPh3). (c) 2006 Elsevier Ltd. All rights reserved.
• ROUSH, WILLIAM R.;KAGEYAMA, MASANORI;RIVA, RENATA;BROWN, BRADLEY B.;WARMU+, J. ORG. CHEM., 56,(1991) N, C. 1192-1210
  作者：ROUSH, WILLIAM R.、KAGEYAMA, MASANORI、RIVA, RENATA、BROWN, BRADLEY B.、WARMU+

  DOI：——

  日期：——