(S)-2-isopropenyl-2-methyl-2,3-dihydrobenzofuran | 190452-78-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: (S)-2-isopropenyl-2-methyl-2,3-dihydrobenzofuran
• 英文别名: (2S)-2-methyl-2-prop-1-en-2-yl-3H-1-benzofuran
• CAS: 190452-78-9
• 化学式: C₁₂H₁₄O
• 分子量: 174.243
• InChiKey: HPIAGBFMTMBOJO-LBPRGKRZSA-N

物化性质

• 沸点：
  239.5±30.0 °C(Predicted)
• 密度：
  1.004±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-2-isopropenyl-2-methyl-2,3-dihydrobenzofuran 在 lithium aluminium tetrahydride 、 氧气 、 臭氧 、 溶剂黄146 、 锌 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 (S)-2-((1RS)-hydroxyethyl)-2-methyl-2,3-dihydrobenzofuran
  参考文献：
  名称：

  3,3'-双取代的2,2'-双（恶唑基）-1,1'-联萘基（boxax）的设计和制备：用于催化不对称瓦克型环化反应的新型手性双（恶唑啉）配体。

  摘要：

  制备了新的旋光的2,2'-双（恶唑基）-1,1'-联萘（boxax），其在C3和C3'位置带有各种取代基（甲氧基羰基，三甲基甲硅烷基，（二甲基氨基）羰基，甲酰基和碘基）恶唑基促进了邻位锂化。在钯（II）催化的邻烯丙基苯酚的Wacker型环化反应中，3,3'-双取代的Boxax配体比3,3'-未取代的配体具有更高的对映选择性。在与（S）-2,2'-双（4,4-二甲基恶唑-2）配位的阳离子钯催化剂存在下（E）-2-（2-甲基-2-丁烯基）苯酚（10）的环化-基）-3，3′-双（甲氧基羰基）-1，1′-联萘基得到96％ee的（S）-2-乙烯基-2-甲基-2，3-二氢苯并呋喃。

  DOI：

  10.1021/jo982104m
• 作为产物：
  描述：

  2-hydroxy-3-(trimethylsilyl)benzaldehyde 在 吡啶 、 咪唑 、 sodium tetrahydroborate 、 N-溴代丁二酰亚胺(NBS) 、 偶氮二甲酸二异丙酯 、 sodium hexamethyldisilazane 、 氟化氢吡啶 、 三苯基膦 、 三氟乙酸 、 三氯氧磷 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 15.5h， 生成 (S)-2-isopropenyl-2-methyl-2,3-dihydrobenzofuran
  参考文献：
  名称：

  Asymmetric Induction via Short-Lived Chiral Enolates with a Chiral C–O Axis

  摘要：

  A novel method has been developed for the asymmetric cyclization of alkyl aryl ethers. The reactions were assumed to proceed via short-lived chiral enolate intermediates with a chiral C-O axis to give cyclic ethers with tetrasubstituted carbon in up to 99% ee. The half-life of racemization of the chiral enolate intermediate was roughly estimated to be similar to 1 s at -78 degrees C.

  DOI：

  10.1021/ja4018122

文献信息

• Atropisomeric bisoxazoline ligands with a bridge across the 5,5′-position of biphenyl for asymmetric catalysis
  作者：Feijun Wang、Yong Jian Zhang、Hao Wei、Jiaming Zhang、Wanbin Zhang

  DOI：10.1016/j.tetlet.2007.04.007

  日期：2007.6

  be retained by macro-ring strain produced by 5,5′-linkage of biphenyls even without 6,6′-substituents on biphenyls. The Pd(II)-2d complex as catalyst showed high catalytic activity and enantioselectivity for asymmetric Wacker-type cyclization of allylphenols.

  已经开发了新的阻转异构的双恶唑啉配体2家族，其具有跨联苯的5,5'-位的桥。即使在联苯上没有6,6'-取代基，也可以通过由联苯的5,5'-连接产生的大环应变来保持此类配体的轴向手性。Pd（II）-2d配合物作为催化剂，对烯丙基酚的不对称Wacker型环化反应具有很高的催化活性和对映选择性。
• Polymer-carrying optically active binaphthyl type oxazoline compound
  申请人：Takasago International Corporation

  公开号：US20040097738A1

  公开（公告）日：2004-05-20

  A polymer-carrying optically active binaphthyl type oxazoline compound having axial asymmetry, represented by the following general formula (1) 1 (wherein R 1 and R 2 may be the same or different from each other and each represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms or the like; R 3 is a hydrogen atom or —R 5 —X—R 6 ; R 4 is a hydrogen atom or the like; R 5 is a straight- or branched-chain aliphatic hydrocarbon chain which may have a directly or indirectly bonded substituent; X is CH 2 , CO 2 , O, CONR 7 or NR 7 ; R 6 is a directly or indirectly bonded polymer; and R 7 is a hydrogen atom or the like), and to a transition metal complex which uses the compound as the ligand.

  一种携带聚合物的具有轴向不对称性的光学活性联萘基氧唑啉化合物，由下列一般式（1）表示（其中R1和R2可以相同也可以不同，且分别表示氢原子、具有1至6个碳原子的烷基基团或类似物；R3表示氢原子或—R5—X—R6；R4表示氢原子或类似物；R5表示可直接或间接连接的直链或支链脂肪烃链，可能具有直接或间接连接的取代基；X为CH2、CO2、O、CONR7或NR7；R6表示直接或间接连接的聚合物；R7表示氢原子或类似物），以及使用该化合物作为配体的过渡金属配合物。
• Chelation-Induced Axially Chiral Palladium Complex System with Tetraoxazoline Ligands for Highly Enantioselective Wacker-Type Cyclization
  作者：Yong Jian Zhang、Feijun Wang、Wanbin Zhang

  DOI：10.1021/jo701469y

  日期：2007.11.1

  A new family of chelation-induced axially chiral palladium complexes by using biphenyl ligands 2 with four identical chiral oxazoline groups at four ortho positions has been developed. Although there is no axial chirality in ligands 2 due to the molecular symmetry, when they chelated with one or two palladium ions, the axial chirality could be induced by destroying the molecular symmetry. Significantly

  通过使用在四个邻位具有四个相同的手性恶唑啉基团的联苯配体2，开发了一个新的螯合诱导的轴向手性钯络合物家族。尽管由于分子对称性而在配体2中没有轴向手性，但是当它们与一个或两个钯离子螯合时，可以通过破坏分子对称性来诱导轴向手性。重要的是，在螯合诱导过程中仅产生一种具有（S）轴构型的非对映体金属配合物。螯合诱导的轴向手性催化体系2c -Pd（CF 3 COO）2 （摩尔比为1：1），在高达99％ee的烯丙基苯酚的Wacker型环化反应中显示出优异的催化活性和对映选择性。
• Highly enantioselective Pd(II)-catalyzed Wacker-type cyclization of 2-allylphenols by use of bisoxazoline ligands with axis-unfixed biphenyl backbone
  作者：Feijun Wang、Yong Jian Zhang、Guoqiang Yang、Wanbin Zhang

  DOI：10.1016/j.tetlet.2007.04.064

  日期：2007.6

  A series of axis-unfixed bisoxazoline ligands with different steric and electronic properties has been synthesized. Due to the different steric interactions, the ligands afforded only one of the two possible diastereomeric Pd(II)-complexes upon metal coordination. The palladium complex (S,aS)-8c showed excellent catalytic activities and enantioselectivities in Wacker-type cyclization of allylphenols with up to 98% ee. (c) 2007 Elsevier Ltd. All rights reserved.
• A simple synthetic approach to homochiral 6- and 6′-substituted 1,1′-binaphthyl derivatives
  作者：Heiko Hocke、Yasuhiro Uozumi

  DOI：10.1016/s0040-4020(02)01584-3

  日期：2003.1

  Various homochiral binaphthyl derivatives having functional groups at the 6-position are important key intermediates for the immobilization of binaphthyl compounds on various solid-supports and have been prepared from commercially available 1,1'-bi-2-naphthol via controlled monopivalation of the 2-hydroxyl group and electrophilic aromatic substitution at the 6-position. (S)-2,2'-Bis-((S)-4-alkyloxazol-2-yl)-6-(2-methoxycarbonyl)ethyl-1,1'-binaphthyls (6-functionalized (S,S)-boxax)) were prepared and immobilized on various polymer supports including PS-PEG, PS, PEGA and MeO-PEG resin. (C) 2003 Elsevier Science Ltd. All rights reserved.