(-)-(R)-2-Methylen-1-cyclohexanol | 68852-11-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(R)-2-Methylen-1-cyclohexanol
• 英文别名: (1R)-2-methylene-1-cyclohexanol；(1R)-2-methylenecyclohexanol；(R)-2-methylenecyclohexanol；2-methylenecyclohexan-1-ol；(1R)-2-methylidenecyclohexan-1-ol
• CAS: 68852-11-9
• 化学式: C₇H₁₂O
• 分子量: 112.172
• InChiKey: GTAPKXQXCYRLRG-SSDOTTSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3-甲氧基环己烯 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 sodium hydroxide 、 碲化氢 、 L-(+)-酒石酸二乙酯 、 4 A molecular sieve 、 sodium formaldehyde sulfoxylate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (-)-(R)-2-Methylen-1-cyclohexanol
  参考文献：
  名称：

  A tellurium transposition route to allylic alcohols: overcoming some limitations of the Sharpless-Katsuki asymmetric epoxidation

  摘要：

  Good yields of enantiomeric allylic alcohols can be obtained in high enantiomeric excess (ee) by combining the Sharpless-Katsuki asymmetric epoxidation process (SAE) with tellurium chemistry. The advantages of the tellurium process are as follows: (1) the 50% yield limitation on the allylic alcohol in the Sharpless kinetic resolution (SKR) can be overcome; (2) allylic tertiary alcohols which are unsatisfactory substrates in the SKR can be obtained in high optical purity; (3) optically active secondary allylic alcohols with tertiary alkyl substituents (e.g. tert-butyl) at C-1 can be obtained in high ee; (4) optically active sterically congested cis secondary alcohols can be obtained in high ee; and (5) the nuisance of the slow SAE of some vinyl carbinols can be avoided. The key step in the reaction sequence is either a stereospecific 1,3-trans position of double bond and alcohol functionalities or an inversion of the alcohol configuration with concomitant deoxygenation of the epoxide function in epoxy alcohols. Trans secondary allylic alcohols can be converted to cis secondary allylic alcohols by way of erythro epoxy alcohols (glycidols); threo glycidyl derivatives are converted to trans secondary allylic alcohols. These transformations are accomplished by the action of telluride ion, generated in situ from the element, on a glycidyl sulfonate ester. Reduction of elemental Te is conveniently done with rongalite (HOCH2SO2Na) in an aqueous medium. This method is satisfactory when Te2- is required to attack a primary carbon site of a glycidyl sulfonate. In cases where Te2- is required to attack a secondary carbon site, reduction of the tellurium must be done with NaBH4 or LiEt3BH. Elemental tellurium is precipitated during the course of the reactions and can be recovered and reused.

  DOI：

  10.1021/jo00055a029

文献信息

• An Efficient Procedure for the 1,3-Transposition of Allylic Alcohols Based on Lithium Naphthalenide Induced Reductive Elimination of Epoxy Mesylates
  作者：Hsing-Jang Liu、Jia-Liang Zhu、Yen-Ku Wu

  DOI：10.1055/s-2008-1032092

  日期：——

  An efficient protocol for the 1,3-transposition of allylic alcohols has been developed. The method is based on the pretransformation of allylic alcohols into the corresponding epoxy mesylates, followed by the reductive elimination of the resulting epoxy mesylates by using lithium naphthalenide (LN) as a reducing agent.

  高效实现烯丙醇1,3-反式转位的协议已被开发出来。该方法基于烯丙醇预转化为其相应的环氧甲磺酸酯，随后利用萘锂（LN）作为还原剂对所生成的环氧甲磺酸酯进行还原消除。
• Allylic alcohols by methylene transfer from N-lithiomethyl-N,N′,N″,N″-tetramethyldiethylenetriamine to epoxides
  作者：Marius Schakel、Hendrikus Luitjes、Frank L. M. Dewever、Jan Scheele、Gerhard W. Klumpp

  DOI：10.1039/c39950000513

  日期：——

  Allylic (homoallylic) alcohols are obtained from epoxides (and certain oxetanes) and N-lithiomethyl-N,N′,N″,N″-tetramethyldiethylenetriamine.

  烯丙基（均烯丙基）醇可从环氧化物（和某些氧杂环丁烷）和 N-硫甲基-N,N²,Nâ³,Nâ³-四甲基二乙烯三胺中获得。
• Solvolytic hydroperoxide rearrangements IV. Selective rearrangement of spiro[5,2]octan-4-ol.
  作者：Robert C. Ronald、Suzanne M. Ruder、Thomas S. Lillie

  DOI：10.1016/s0040-4039(00)95667-3

  日期：1987.1

  Rearrangement of spiro[5,2]octan-4-ol, 1, in acidified THF-H2O2 is a selective process in which substitution occurs with retention of configuration and ring-expansion with inversion of the carbinyl center.

  螺[5,2] octan-4-ol，1在酸化的THF-H 2 O 2中的重排是一种选择性过程，其中取代发生且保留构型，而环扩展与羰基中心倒置。
• Novel Catalytic Kinetic Resolution of Racemic Epoxides to Allylic Alcohols
  作者：Arnaud Gayet、Sophie Bertilsson、Pher G. Andersson

  DOI：10.1021/ol025983e

  日期：2002.10.1

  [formula: see text] The kinetic resolution of racemic epoxides via catalytic enantioselective rearrangement to allylic alcohols was investigated. Using the Li-salt of (1S,3R,4R)-3-(pyrrolidinyl)methyl-2-azabicyclo [2.2.1] heptane 1 as catalyst allowed both epoxides and allylic alcohols to be obtained in an enantioenriched form.

  研究了外消旋环氧化物通过催化对映选择性重排为烯丙基醇的动力学拆分。使用（1S，3R，4R）-3-（吡咯烷基）甲基-2-氮杂双环[2.2.1]庚烷1的锂盐作为催化剂，可以得到对映体富集形式的环氧化物和烯丙基醇。
• A Stereochemical Study of the Isomerization of Cyclopropyl Ethers to Allyl Ethers Catalyzed with Zinc Iodide
  作者：Takashi Sugimura、Tohru Futagawa、Atsushi Mori、Ilhyong Ryu、Noboru Sonoda、Akira Tai

  DOI：10.1021/jo960448b

  日期：1996.1.1

  Optically active 1-alkoxybicyclo[4.1.0]heptane was converted using zinc iodide as a catalyst to 2-alkoxymethylidenecyclohexane without loss of optical purity. The mechanism of the isomerization was studied using a stereochemical analysis of the product and deuterium labeling experiments. The results indicated that the isomerization takes place through a stepwise mechanism that involves an attack of

  使用碘化锌作为催化剂将旋光的1-烷氧基双环[4.1.0]庚烷转化为2-烷氧基亚甲基环己烷，而不会损失光学纯度。使用产物的立体化学分析和氘标记实验研究了异构化的机理。结果表明，异构化是通过逐步机理进行的，该逐步机理涉及碘化锌攻击环丙烷环以引起开环，随后分子内的1,2-氢化物移位并释放出碘化锌。