(S)-(-)-Z-3-penten-2-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-(-)-Z-3-penten-2-ol
• 英文别名: (2S,3Z)-3-penten-2-ol；(S)-(Z)-pent-3-en-2-ol；2(S)-hydroxy-cis-3-butene；(A+/-)-cis-pent-3-en-2-ol；(Z,2S)-pent-3-en-2-ol
• 化学式: C₅H₁₀O
• 分子量: 86.1338
• InChiKey: GJYMQFMQRRNLCY-XUELKZDXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-(-)-Z-3-penten-2-ol 在 咪唑 、 次氯酸叔丁酯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 22.0h， 生成 (4R,5S)-3-[(R)-2-(tert-Butyl-dimethyl-silanyloxy)-1-methyl-ethyl]-5-[(S)-1-(tert-butyl-diphenyl-silanyloxy)-ethyl]-4-methyl-4,5-dihydro-isoxazole
  参考文献：
  名称：

  Stereochemically Rich Pentaketides from Bis(isoxazolines):  A General Strategy for Efficient Polyketide Synthesis

  摘要：

  A strategy based on diastereoselective dipolar cycloaddition reaction of nitrile oxides and allylic alcoholates has been applied to the synthesis of bis(isoxazolines) that are precursors to polyketide fragments. These intermediates can be elaborated into protected polyols by chemoselective reductive opening of each isoxazoline sequentially or, alternatively, both simultaneously, potentially providing access to all stereoisomers of this carbon skeleton.

  DOI：

  10.1021/ol0490633
• 作为产物：
  描述：

  戊-3-炔-2-酮 在 Lindlar's catalyst 喹啉 、 氢气 、 2-蒎烯聚合物 、 9-硼双环[3.3.1]壬烷 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 生成 (S)-(-)-Z-3-penten-2-ol
  参考文献：
  名称：

  Palladium(II)-Catalyzed Exchange and Isomerization Reactions. 17. Exchange of Chiral Allyl Alcohols with Hydroxide, Methoxide, and Phenyl at High [Cl^-]. Stereochemistry of the Wacker Reaction

  摘要：

  At high [Cl-] (> 2.0 M), PdCl42- catalyzes the exchange of chiral allylic alcohols with hydroxy, methoxy, and phenyl to give chiral allyl-substituted olefins. With unsymmetrical olefins, isomerization occurs along with exchange. The hydroxyl exchange occurs in aqueous solution while the other exchanges are carried out in methanol solution. At low [Cl-] (0.1 M) oxidation to the corresponding beta-hydroxy-, methoxy-, and phenyl-substituted carbonyl compounds occurred. The absolute configurations of the oxidation and exchange products should be the same if the same mode of addition to the Pd(II)-pi-complex is operative. The absolute configurations of the oxidation and exchange products for the phenylation reaction were the same, while for hydroxy and methoxy they were different. This result indicates methanol and water must have different stereochemistries of addition at high and low [Cl-]. Thus, previous studies showing anti hydroxypalladation at high [Cl-] are not valid indicators of the stereochemistry at low [Cl-]. If anti addition occurs at high [Cl-], the addition must be syn at low [Cl-].

  DOI：

  10.1021/jo9906274

文献信息

• Succinoylamino hydroxyethylamino sulfonyl urea derivatives useful as retroviral protease inhibitors
  申请人：G.D. Searle & Co.

  公开号：US06337398B1

  公开（公告）日：2002-01-08

  Succinoylamino hydroxyethylamino sulfonyl urea derivatives of the formula: wherein the substituents are as defined in the specification, are effective as retroviral protease inhibitors, and in particular as inhibitors of HIV protease.

  丁酰氨基羟基乙氨基磺酰脲衍生物的公式如下： 其中，取代基的定义如说明书所述，这些衍生物作为逆转录病毒蛋白酶抑制剂是有效的，尤其是作为HIV蛋白酶的抑制剂。
• Palladium(II)-catalyzed dicarboxymethylation of chiral allylic alcohols: chirality transfer affording optically active diesters containing three contiguous chiral centers
  作者：Othman Hamed、Patrick M. Henry、Daniel P. Becker

  DOI：10.1016/j.tetlet.2010.04.105

  日期：2010.7

  This manuscript describes the extension of Stille’s palladium-catalyzed olefin dicarbonylation reaction to chiral allylic alcohols with chirality transfer to afford the corresponding chiral alcohol functionalized with bis-carbomethoxy esters, containing three contiguous chiral centers, in good to excellent diastereoselectivities (78–98%).

  该手稿描述了Stille的钯催化的烯烃二羰基化反应扩展到具有手性转移的手性烯丙基醇，从而得到相应的被双碳甲氧基酯官能化的手性醇，该手性醇包含三个连续的手性中心，具有良好的至优异的非对映选择性（78-98％） 。
• Synthesis of the Active Form of Loxoprofen by Using Allylic Substitutions in Two Steps
  作者：Tomonori Hyodo、Yohei Kiyotsuka、Yuichi Kobayashi

  DOI：10.1021/ol802949c

  日期：2009.3.5

  High regioselectivity for allylic substitution of the cyclopentenyl picolinate 5 with benzylcopper reagent was attained with ZnBr2, and the finding was applied to the p-BrC6H4CH2 reagent. The cyclopentene moiety in the product was reduced to the cyclopentane, and the p-BrC6H4 was converted to the “Cu”C6H4 for the second allylic substitution with picolinate 8 to furnish the title compound after oxidative

  用ZnBr 2获得高苄基选择性地用苄基铜试剂对环戊烯基吡啶甲酸5进行烯丙基取代，并将该发现应用于对-BrC 6 H 4 CH 2试剂。将产物中的环戊烯部分还原为环戊烷，将p -BrC 6 H 4转化为“ Cu” C 6 H 4，用吡啶甲酸8进行第二次烯丙基取代，以氧化裂解所得产物得到标题化合物烯烃部分。
• Highly Stereoselective C–C Bond Formation by Rhodium-Catalyzed Tandem Ylide Formation/[2,3]-Sigmatropic Rearrangement between Donor/Acceptor Carbenoids and Chiral Allylic Alcohols
  作者：Zhanjie Li、Brendan T. Parr、Huw M. L. Davies

  DOI：10.1021/ja303023n

  日期：2012.7.4

  The tandem ylide formation/[2,3]-sigmatropic rearrangement between donor/acceptor rhodium carbenoids and chiral allyl alcohols is a convergent C-C bond forming process, which generates two vicinal stereogenic centers. Any of the four possible stereoisomers can be selectively synthesized by appropriate combination of the chiral catalyst Rh(2)(DOSP)(4) and the chiral alcohol.

  供体/受体铑卡宾和手性烯丙醇之间的串联叶立德形成/[2,3]-sigmatropic重排是一个收敛的CC键形成过程，产生两个邻位立体中心。通过手性催化剂Rh(2)(DOSP)(4)和手性醇的适当组合，可以选择性地合成四种可能的立体异构体中的任何一种。
• A General Solution to the Modular Synthesis of Polyketide Building Blocks by Kanemasa Hydroxy-Directed Nitrile Oxide Cycloadditions
  作者：Jeffrey W. Bode、Nina Fraefel、Dieter Muri、Erick M. Carreira

  DOI：10.1002/1521-3773(20010601)40:11<2082::aid-anie2082>3.0.co;2-1

  日期：2001.6.1

  starting materials suffice for the modular synthesis of all possible polypropionate diastereomers. This general method for the diastereoselective synthesis of syn, anti, and methyl ketone aldol adducts utilizes a powerful MgII -mediated, hydroxy-directed nitrile oxide cycloaddition. The free hydroxy group provides an ideal synthetic handle enabling the rapid assembly of complex polyketide structures

  单一，便捷的反应方案和易于获得的同一套起始原料就足以用于所有可能的聚丙烯酸酯非对映异构体的模块合成。这种非对映选择性合成顺式，反式和甲基酮醛醇醛加合物的通用方法利用了功能强大的Mg II介导的，羟基定向的丁腈氧化物环加成反应。游离羟基提供了理想的合成手感，能够快速组装复杂的聚酮化合物结构。TBS = tBuMe 2 Si。