2-hydroxy-2,6-dimethylhept-5-enenitrile | 27886-25-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-hydroxy-2,6-dimethylhept-5-enenitrile
• 英文别名: 2-Hydroxy-2,6-dimethyl-hept-5-ennitril
• CAS: 27886-25-5
• 化学式: C₉H₁₅NO
• 分子量: 153.224
• InChiKey: FROHVQGVFUDCRI-UHFFFAOYSA-N

物化性质

• 沸点：
  115-117 °C(Press: 2 Torr)
• 密度：
  0.9224 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-hydroxy-2,6-dimethylhept-5-enenitrile 在 mercury(II) trifluoroacetate 、 碳酸氢钠 、 potassium bromide 、 吡啶 、 溴 作用下， 以 乙腈 为溶剂， 生成 (2S,5R)-5-Bromo-2,6,6-trimethyl-tetrahydro-pyran-2-carbonitrile
  参考文献：
  名称：

  Total Synthesis of Thyrsiferyl 23-Acetate, a Specific Inhibitor of Protein Phosphatase 2A and an Anti-Leukemic Inducer of Apoptosis

  摘要：

  A convergent synthetic entry to the squalenoid polyether system has been developed and applied to the biologically active marine natural products thyrsiferyl 23-acetate (la), thyrsiferol (Ib), thyrsiferyl 18-acetate (Ic), and thyrsiferyl 18,23-diacetate (Id). This involved the separate construction of two advanced intermediates representing the C1-C15 (4) and C16-C24 (5) domains, followed by their organochromium-mediated coupling, installation of the tertiary alcohol at C15, and manipulation of the C18 and C23 acetate moieties. The C1-C15 (4) intermediate containing the three tetrahydropyranyl rings (A-B-C) was derived from two preconstructed tetrahydropyran-containing units representing the functionalized A (C2-C6) and C (C10-C14) rings (6 and 7, respectively). The bromotetrahydropyranyl A ring was obtained via bromoetherification of the hydroxyalkene 16, which was synthesized from (2R,3R)-epoxy geraniol. The C ring was stereoselectively constructed by acid-catalyzed opening of the hydroxy epoxide 32, derived from D-glutamic acid. Intermediates 6 and 7 were-joined using organochromium conditions, and ketone and hydroxyl functionalities were installed at carbons:7 and 11, respectively. Closure of the B ring was accomplished stereoselectively by formation of species derived from a C7, C11 keto-alcohol and in situ reduction of a tetrahydropyranyl oxonium. The complementary tetrahydrofuran D (C19-C22) ring was obtained from a geraniol-derived tertiary hydroxy alkene (44) via a stereoselective Re(VII)-induced syn-oxidative cyclization. The side chain appended to the D ring was elaborated into trans-alkenyl iodide 5 under Takai reaction conditions. CrCl2-mediated coupling of aldehyde 4 containing the secondary bromide at C3 of the natural products, with iodide 5 bearing acetate moieties at C18 and C23, installed the C15-C16 carbon-carbon bond. The resultant C15 allylic carbinol was converted into an cr,P-saturated ketone, and the final methyl group was added stereoselectively using methylmagnesium bromide. Saponification of the C18 acetate yielded la, whereas cleavage of both C18 and C23 acetates gave the triol Ib. This modular entry into the squalenoid-polyether system may facilitate further evaluation of the antileukemic, apoptosis-inducing, protein serine/threonine phosphatase 2A inhibitory and anti-multidrug resistance activities of the thyrsiferol-derived natural products.

  DOI：

  10.1021/ja000001r
• 作为产物：
  描述：

  三甲基氰硅烷 、 6-甲基-5-庚烯-2-酮 在 四氯化钛 、 盐酸 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 1.0h， 生成 2-hydroxy-2,6-dimethylhept-5-enenitrile
  参考文献：
  名称：

  Copper-Catalyzed 1,2-Aminocyanation of Unactivated Alkenes via Cyano Migration

  摘要：

  A copper-catalyzed aminocyanation of alkenes has been achieved through distal cyano migration using O-benzoylhydroxylamines and N-fluorobenzenesulfonimides. This method offers a rapid approach to generate diverse beta-amino and beta-sulfonimido nitriles. These reactions feature mild conditions, tolerance of sensitive functional groups, and excellent regioselectivity. Mechanistic studies suggest that these transformations are initiated by a copper-catalyzed amination step followed by a cyano migration step.

  DOI：

  10.1021/acs.orglett.0c01217

文献信息

• Colonge; Lagier, Bulletin de la Societe Chimique de France, 1949, p. 16
  作者：Colonge、Lagier

  DOI：——

  日期：——
• Werner; Bogert, Journal of Organic Chemistry, 1938, vol. 3, p. 586
  作者：Werner、Bogert

  DOI：——

  日期：——
• Copper-Catalyzed 1,2-Aminocyanation of Unactivated Alkenes via Cyano Migration
  作者：Yungeun Kwon、Qiu Wang

  DOI：10.1021/acs.orglett.0c01217

  日期：2020.6.5

  A copper-catalyzed aminocyanation of alkenes has been achieved through distal cyano migration using O-benzoylhydroxylamines and N-fluorobenzenesulfonimides. This method offers a rapid approach to generate diverse beta-amino and beta-sulfonimido nitriles. These reactions feature mild conditions, tolerance of sensitive functional groups, and excellent regioselectivity. Mechanistic studies suggest that these transformations are initiated by a copper-catalyzed amination step followed by a cyano migration step.
• Total Synthesis of Thyrsiferyl 23-Acetate, a Specific Inhibitor of Protein Phosphatase 2A and an Anti-Leukemic Inducer of Apoptosis
  作者：Isabel C. González、Craig J. Forsyth

  DOI：10.1021/ja000001r

  日期：2000.9.1

  A convergent synthetic entry to the squalenoid polyether system has been developed and applied to the biologically active marine natural products thyrsiferyl 23-acetate (la), thyrsiferol (Ib), thyrsiferyl 18-acetate (Ic), and thyrsiferyl 18,23-diacetate (Id). This involved the separate construction of two advanced intermediates representing the C1-C15 (4) and C16-C24 (5) domains, followed by their organochromium-mediated coupling, installation of the tertiary alcohol at C15, and manipulation of the C18 and C23 acetate moieties. The C1-C15 (4) intermediate containing the three tetrahydropyranyl rings (A-B-C) was derived from two preconstructed tetrahydropyran-containing units representing the functionalized A (C2-C6) and C (C10-C14) rings (6 and 7, respectively). The bromotetrahydropyranyl A ring was obtained via bromoetherification of the hydroxyalkene 16, which was synthesized from (2R,3R)-epoxy geraniol. The C ring was stereoselectively constructed by acid-catalyzed opening of the hydroxy epoxide 32, derived from D-glutamic acid. Intermediates 6 and 7 were-joined using organochromium conditions, and ketone and hydroxyl functionalities were installed at carbons:7 and 11, respectively. Closure of the B ring was accomplished stereoselectively by formation of species derived from a C7, C11 keto-alcohol and in situ reduction of a tetrahydropyranyl oxonium. The complementary tetrahydrofuran D (C19-C22) ring was obtained from a geraniol-derived tertiary hydroxy alkene (44) via a stereoselective Re(VII)-induced syn-oxidative cyclization. The side chain appended to the D ring was elaborated into trans-alkenyl iodide 5 under Takai reaction conditions. CrCl2-mediated coupling of aldehyde 4 containing the secondary bromide at C3 of the natural products, with iodide 5 bearing acetate moieties at C18 and C23, installed the C15-C16 carbon-carbon bond. The resultant C15 allylic carbinol was converted into an cr,P-saturated ketone, and the final methyl group was added stereoselectively using methylmagnesium bromide. Saponification of the C18 acetate yielded la, whereas cleavage of both C18 and C23 acetates gave the triol Ib. This modular entry into the squalenoid-polyether system may facilitate further evaluation of the antileukemic, apoptosis-inducing, protein serine/threonine phosphatase 2A inhibitory and anti-multidrug resistance activities of the thyrsiferol-derived natural products.