2-lithio-2-cyclohexen-1-one ethylene ketal | 89279-10-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-lithio-2-cyclohexen-1-one ethylene ketal
• 英文别名: 2-lithio-1-ethylenedioxy-2-cyclohexene
• CAS: 89279-10-7
• 化学式: C₈H₁₁LiO₂
• 分子量: 146.115
• InChiKey: UIPYPIRLLUWRIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.89
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 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-lithio-2-cyclohexen-1-one ethylene ketal 在 Pd-BaSO₄ 硫酸 、 氢气 、 苯硫酚铜(I) 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 1.08h， 生成 2-<4-(trimethylsilyl)-2-butenyl>-2-cyclohexen-1-one
  参考文献：
  名称：

  Cyclooctane or cyclohexane annulations based on intramolecular additions of allylsilanes to conjugated dienones

  摘要：

  The scope and limitations of alkenyl dienone cyclizations for the formation of fused cyclooctane or cyclohexane systems are described.

  DOI：

  10.1021/jo00012a034

文献信息

• Alternation of stereocontrol mode in the cyclization of 2-(3′-4′-dimethyl-6′-trimethylsilyl-4′-hexenyl)-2-cyclohexenones by the auxiliary controlling substituents at 1′- and 2′-positions of the side chain
  作者：Takashi Tokorayama、Masashi Kato、Takehiko Aoto、Taeko Hattori、Hideo Iio、Yoshihiko Odagaki

  DOI：10.1016/0040-4039(94)88294-0

  日期：1994.10

  stereochemical mode in the cyclization of the title compound the diastereoselectivities in that of the substrates with an oxy-substituent at 1′ and 2′ positions of the side chain were investigated. In the cyclization of the substrate with the 2′-oxy-substituent its controlling effect was not enough to reverse the diastereoselectivity. On the other hand the cyclization of the substrates with the 1′-oxy-substituent

  为了改变标题化合物环化中的立体化学模式，研究了在侧链的1'和2'位置带有氧取代基的底物的非对映选择性。在具有2'-氧基取代基的底物环化中，其控制作用不足以逆转非对映选择性。另一方面，在其随后消除的情况下，用1'-氧基取代基对底物进行环化，得到具有多种立体化学结果的八氢萘衍生物。通过关于氧取代基和路易斯酸的种类和立体化学的选择，四种非对映异构体的各自的立体选择性形成，包括具有8,9-反式的八酮衍生物的四种非对映异构体获得了-二甲基构型。
• Selective mono- and polymethylene homologations of copper reagents using (iodomethyl)zinc iodide
  作者：AchyuthaRao Sidduri、Michael J. Rozema、Paul Knochel

  DOI：10.1021/jo00062a010

  日期：1993.5

  A wide range of unsaturated aryl-, alkenyl-, alkynylcopper compounds can be selectively homologated by a methylene unit using (iodomethyl)zinc iodide or bis(iodomethyl)zinc. These reactions allow the generation of mixed allylic zinc-copper compounds which can be efficiently trapped with carbonyl compounds. An application to a general preparation of functionalized alpha-methylene-gamma-butyrolactones is described. The homologation of alkynylcoppers with (iodomethyl)zinc iodide allows a one-pot preparation of propargylic copper reagents which in the presence of a carbonyl compound provide various homopropargylic alcohols in excellent yields. In the absence of an electrophile, a clean quadruple methylene homologation of alkynylcoppers occurs to furnish dienic copper reagents. The homologation of other types of copper reagents is also possible, and carbanions at the alpha-position to amines as well as homoenolates of aldehydes or ketones can also be prepared by this method.
• Tandem Oxy-Cope/Transannular Ene Reaction of 1,2-Divinylcyclohexanols
  作者：Jeffrey M. Warrington、Glenn P. A. Yap、Louis Barriault

  DOI：10.1021/ol005502w

  日期：2000.3.1

  [GRAPHICS]The syntheses via tandem oxy-Cope/transannular ene reaction of 1,2-divinylcyclohexanols to bi- and tricyclic skeletons are described, This strategy generates a rapid method for the preparation of advanced polycyclic intermediates with high diastereoselectivity.
• C(1)-Substituted menthol derivatives: Self-removing chiral auxiliaries for asymmetric conjugate additions to cycloalkenones
  作者：Raymond L. Funk、Ge Yang

  DOI：10.1016/s0040-4039(98)02627-6

  日期：1999.2

  C(1)-substituted (-)-menthone derivatives 3 were prepared by the stereoselective addition of the alkenyllithium reagents 9 to menthone (8) and subsequent acid catalyzed hydrolysis of the dioxolane protecting groups. Conjugate addition of cuprate reagents to enones 3a,b followed by a methanol quench directly gave the beta-alkylcycloalkanones 7 via retro-aldol reactions in 80-91% ee. (C) 1999 Elsevier Science Ltd. All rights reserved.
• MAJETICH, GEORGE;HULL, KENNETH;CASARES, ADA M.;KHETANI, VIKRAM, J. ORG. CHEM., 56,(1991) N2, C. 3958-3973
  作者：MAJETICH, GEORGE、HULL, KENNETH、CASARES, ADA M.、KHETANI, VIKRAM

  DOI：——

  日期：——