(S)-1-(thiophen-2-yl)-but-3-en-1-ol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (S)-1-(thiophen-2-yl)-but-3-en-1-ol
• 英文别名: 1-(thiophen-2-yl)but-3-en-1-ol；(S)-(-)-1-(2-thienyl)but-3-en-1-ol；(S)-1-(2-thienyl)-3-buten-1-ol；(1S)-1-thiophen-2-ylbut-3-en-1-ol
• 化学式: C₈H₁₀OS
• 分子量: 154.233
• InChiKey: KRBDYAKQPULVNR-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  48.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-1-(thiophen-2-yl)-but-3-en-1-ol 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 (3R,4aS)-3-(thiophen-2-yl)-2-tosyl-3,4,4a,5-tetrahydro-1H-cyclopenta[c] pyridin-6(2H)-one
  参考文献：
  名称：

  Stereoselective synthesis of optically active cyclopenta[c]pyridines and tetrahydropyridines

  摘要：

  The intramolecular Pauson-Khand and ring closing metathesis (RCM) reactions of nitrogen containing chiral enynes and dienes are described. The enyne and diene systems comprised of N-propargylated and N-allylated units are constructed on chiral homoallylic or homopropargylic alcohol backbones, respectively, via S(N)2 and/or modified Mitsunobu reactions. The racemic homoallylic and homopropargylic alcohol derivatives were successfully resolved in high ee (93-99%) by applying chemoenzymatic methods using various lipases such as PS-C II, Lipozyme, and CAL-B. Each enantiomerically enriched enyne afforded the most conformationally stable diastereomeric cyclopenta[c]pyridine ring system as the sole product, whereas enantiomerically enriched dienes gave tetrahydropyridine derivatives as a result of intramolecular Pauson-Khand and RCM reactions, respectively. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.04.016
• 作为产物：
  描述：

  2-噻吩甲醛 在 indium 、 Pseudomonas cepacia lipase immobilized on modified ceramic 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 30.0h， 生成 (S)-1-(thiophen-2-yl)-but-3-en-1-ol
  参考文献：
  名称：

  化学酶法合成旋光性杂环​​均烯丙基和均丙炔醇

  摘要：

  已开发出一种化学酶学方法，该方法是在水性介质中使用铟介导的杂环醛的烯丙基化烯丙基化，然后在有机介质中假单胞菌cepcia脂肪酶催化外消旋均烯丙基和均炔丙醇的对映选择性酰化。观察到，与天然酶（PS Amano）相比，固定在陶瓷颗粒上的脂肪酶（PS-C Amano II）以更少的时间以高对映选择性的方式催化拆分。该方法提供了新的功能化手性合成子，可用于合成天然和假天然产物。

  DOI：

  10.1016/s0957-4166(02)00743-7

文献信息

• Chiral Bis(imidazolinyl)phenyl NCN Pincer Rhodium(III) Catalysts for Enantioselective Allylation of Aldehydes and Carbonyl–Ene Reaction of Trifluoropyruvates
  作者：Tao Wang、Xin-Qi Hao、Juan-Juan Huang、Jun-Long Niu、Jun-Fang Gong、Mao-Ping Song

  DOI：10.1021/jo4014194

  日期：2013.9.6

  Chiral NCN pincer rhodium(III) complexes with bis(imidazolinyl)phenyl ligands were found to be effective catalysts for the allylation of a variety of electronically and structurally diverse aldehydes with allyltributyltin, giving the corresponding optically active homoallylic alcohols in high yields with enantioselectivities of up to 97% ee. These complexes were also applied in the carbonyl–ene reaction

  发现具有双（咪唑啉基）苯基配体的手性NCN钳形铑（III）配合物是有效的催化剂，用于将各种电子和结构不同的醛与烯丙基三丁基锡进行烯丙基化，从而以高收率得到相应的光学活性均烯醇，且对映选择性高达到97％ee。这些配合物还用于三氟丙酮酸乙酯或三氟丙酮酸甲酯与各种2-芳基丙烯的羰基-烯反应中。借助三氟甲磺酸银，钳型铑（III）催化剂可以催化反应，以高收率和高立体选择性（最高95％ee）提供相应的手性α-羟基-α-三氟甲基酯。
• Structure influence of chiral 1,1′-biscarboline-N,N′-dioxide on the enantioselective allylation of aldehydes with allyltrichlorosilanes
  作者：Bing Bai、Hua-Jie Zhu、Wei Pan

  DOI：10.1016/j.tet.2012.06.042

  日期：2012.8

  A series of new axially chiral 1,1′-biscarboline-N,N′-dioxide Lewis base organocatalysts were examined in the asymmetric allylation of aldehydes with allyltrichlorosilane. The chiral catalysts (R)-1a–e bearing ester groups in 3,3′ position provided good yields of the homoallyl alcohols with excellent enantioselectivities up to 99% for a broad substrate scope that covers aliphatic, aromatic, heteroaromatic

  在醛与烯丙基三氯硅烷的不对称烯丙基化反应中，研究了一系列新型的轴向手性1,1'-双咔啉-N，N'-二氧化物路易斯碱有机催化剂。的手性催化剂（[R ）- 1A - ë轴承酯基团在3,3'位置上设置具有优异的对映选择性高达99％的高烯丙基醇的良好的产率为广泛的底物范围，其覆盖脂族，芳香族，杂芳香族，和α，β -不饱和醛。阐明了溶剂对转化率和对映选择性的影响，并确定了CH 2 Cl 2被证明是反应的最佳溶剂。另外，还探索了与巴豆基三氯硅烷的烯丙基化反应，结果表明，（E）-巴豆基三氯硅烷具有较好的非对映选择性，有利于其抗异构体的形成。
• Chiral Unsymmetrically Substituted Bipyridine <i>N</i> ,<i>N′</i> -Dioxides as Catalysts for the Allylation of Aldehydes
  作者：Jan Ulč、David Nečas、Petr Koukal、Vojtěch Havlíček、Zdeněk Tošner、Simona Hybelbauerová、Martin Kotora

  DOI：10.1002/ejoc.201800485

  日期：2018.10.9

  A series of unsymmetrically substituted diastereoisomeric (Ra,R) and (Sa,R) bipyridine N,N′‐dioxides were tested as catalysts for the enantioselective allylation of various aldehydes. Homoallylic alcohols were obtained with enantiopurities of up to 99 % ee.

  测试了一系列不对称取代的非对映异构体（R a，R）和（S a，R）联吡啶N，N'-二氧化物作为各种醛的对映选择性烯丙基化的催化剂。得到的对映纯度高达99％ee的均烯丙基醇。
• Synthetically amenable amide derivatives of tosylated-amino acids as organocatalysts for enantioselective allylation of aldehydes: computational rationale for enantioselectivity
  作者：Debashis Ghosh、Debashis Sahu、S. Saravanan、Sayed H. R. Abdi、Bishwajit Ganguly、Noor-ul H. Khan、Rukhsana I. Kureshy、Hari C. Bajaj

  DOI：10.1039/c3ob27513b

  日期：——

  A phenylalanine derived chiral amide is developed that serves as an effective organocatalyst for the reaction of allyltrichlorosilane with aryl, hetero-aryl and α,β-unsaturated aldehydes to afford the desired homoallylic alcohols in good yield (up to 90%) and high enantioselectivity (up to 99%). The experimental results and DFT calculations suggest that para substituted aromatic aldehydes as substrate show higher ee in the product than their ortho/meta counterparts. The 1H and 13C NMR spectra study corroborated the calculated results. The chiral organocatalyst can be easily synthesized from optically pure phenylalanine in two simple steps with 90% overall yield.

  开发了一种由苯丙氨酸衍生的手性酰胺，它作为有效的有机催化剂，用于烯丙基三氯硅烷与芳基、杂芳基和α,β-不饱和醛的反应，以良好的产率（高达90%）和高对映选择性（高达99%）得到所需的同烯丙基醇。实验结果和DFT计算表明，与邻/间位取代的芳香醛相比，对位取代的芳香醛作为底物在产物中显示出更高的对映体过量值。1H和13C NMR光谱学研究证实了计算结果。手性有机催化剂可以通过两个简单步骤从光学纯苯丙氨酸轻松合成，总产率为90%。
• Oxazoline derivatives tagged with tosylated amino acids as recyclable organocatalysts for enantioselective allylation of aldehydes
  作者：Debashis Ghosh、Arghya Sadhukhan、Nabin Ch. Maity、Sayed H. R. Abdi、Noor-ul H. Khan、Rukhsana I. Kureshy、Hari C. Bajaj

  DOI：10.1039/c3ra47424k

  日期：——

  of amino acid-based oxazoline compounds have been prepared and successfully applied to the enantioselective allylation reaction of aldehydes. The fine-tuning of the structure of the oxazolines led to (S,S)-4 as an efficient organocatalyst which gave homoallyl alcohols in good yield (up to 90%) and excellent ee (up to 99%) for a wide range of substrates including aromatic, hetero-aromatic and α,β-unsaturated

  已经制备了一系列基于氨基酸的恶唑啉化合物并将其成功地用于醛的对映选择性烯丙基化反应。恶唑啉结构的微调导致了（S，S）-4作为一种有效的有机催化剂，在很宽的范围内都能得到高收率（高达90％）和良好的ee（高达99％）的均烯丙基醇。底物包括芳族，杂芳族和α，β-不饱和醛。通过三个简单的步骤合成了手性有机催化剂，总收率达88％，并成功地回收了多达三个循环。根据实验观察结果和NMR研究，提出了该反应的可能机理。