(S)-1,4-diphenyl-2-hydroxy-4-penten-1-one

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (S)-1,4-diphenyl-2-hydroxy-4-penten-1-one
• 英文别名: 1,4-diphenyl-2-hydroxy-4-penten-1-one；2-hydroxy-1,4-diphenyl-4-penten-1-one；(2S)-2-hydroxy-1,4-diphenylpent-4-en-1-one
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: CQEASWAGCLDBMS-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  丙醛 、 (S)-1,4-diphenyl-2-hydroxy-4-penten-1-one 在 iron(III) chloride 、 叔丁基二甲基氯硅烷 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  Completely OH-Selective FeCl₃-Catalyzed Prins Cyclization: Highly Stereoselective Synthesis of 4-OH-Tetrahydropyrans

  摘要：

  The completely OH-selective Prins cyclization has been realized from the enantioselective ene reaction product. A variety of 4-hydroxyl-tetrahydropyrans were exclusively generated via FeCl3-catalyzed Prins reaction. Excellent stereoselectivities (up to >99:1 dr and >99.5:0.5 er) were obtained for a remarkably broad range of substrates under mild reaction conditions. The control experiments, including NOE effects and O-18-labeling studies, as well as DFT calculations were conducted to provide fundamental insights into the mechanism of the reaction. A different [2 + 2] cycloaddition process was suggested to rationalize the observed OH-selectivity.

  DOI：

  10.1021/ja3062002
• 作为产物：
  描述：

  苯基丙醇水合物 、 2-苯基-1-丙烯 在 (2S)-N-[2,6-di(propan-2-yl)phenyl]-1-[3-[(2S)-2-[[2,6-di(propan-2-yl)phenyl]carbamoyl]-1-oxidopiperidin-1-ium-1-yl]propyl]-1-oxidopiperidin-1-ium-2-carboxamide 、 nickel(II) tetrafluoroborate hexahydrate 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以98%的产率得到(S)-1,4-diphenyl-2-hydroxy-4-penten-1-one
  参考文献：
  名称：

  Completely OH-Selective FeCl₃-Catalyzed Prins Cyclization: Highly Stereoselective Synthesis of 4-OH-Tetrahydropyrans

  摘要：

  The completely OH-selective Prins cyclization has been realized from the enantioselective ene reaction product. A variety of 4-hydroxyl-tetrahydropyrans were exclusively generated via FeCl3-catalyzed Prins reaction. Excellent stereoselectivities (up to >99:1 dr and >99.5:0.5 er) were obtained for a remarkably broad range of substrates under mild reaction conditions. The control experiments, including NOE effects and O-18-labeling studies, as well as DFT calculations were conducted to provide fundamental insights into the mechanism of the reaction. A different [2 + 2] cycloaddition process was suggested to rationalize the observed OH-selectivity.

  DOI：

  10.1021/ja3062002

文献信息

• Palladium(II) Complexes of C2-Bridged Chiral Diphosphines: Application to Enantioselective Carbonyl-Ene Reactions
  作者：He-Kuan Luo、Yuan-Ling Woo、Herbert Schumann、Chacko Jacob、Martin van Meurs、Hai-Yan Yang、Yen-Ting Tan

  DOI：10.1002/adsc.200900888

  日期：——

  2R,2′R)‐1,1′‐bis(1,1‐dimethylethyl)‐2,2′‐biphospholane [(S,S,R,R)‐TANGPHOS] and (2R,2′R,5R,5′R)‐1,1′‐(1,2‐phenylene)bis[2,5‐bis(1‐methylethyl)phospholane] [(R,R)‐i‐Pr‐DUPHOS] are C2‐bridged chiral diphosphines that form stable complexes with palladium(II) and platinum(II) containing a five‐membered chelate ring. The Pd(II)‐BINAPHANE catalyst displayed good to excellent enantioselectivities with ee

  （11b R，11'b R）‐4,4′‐（1,2-苯撑）双[4,5‐dihydro‐3 H ‐ dinaphtho [2,1 ‐ c：1′，2′‐ e ] ] [简称为（- [R）-BINAPHANE]，（3 - [R，3' - [R，4小号，4'小号，11B小号，11'B小号）-4,4'-双（1,1-二甲基乙基）-4- ，4'，5,5'-tetrahydro‐3,3'-bi‐3 H -dinaphtho [2,1- c：1'，2'- e ] phosphePIn [（S）-BINAPINE]，（1 S， 1'小号，2 - [R，2' - [R）-1,1'-双（1,1-二甲基乙基）-2,2'- biphospholane [（S，S，R，R）-TangPhos]和（2 - [R，2' - [R，5 - [R，5' - [R）-1,1' - （1,2-亚苯基）双[2,5-双（1-甲基乙基）磷杂环戊烷]
• Enantioselective Carbonyl-Ene Reactions of Arylglyoxals with a Chiral Palladium(II)-BINAP Catalyst
  作者：He-Kuan Luo、Lim Bee Khim、Herbert Schumann、Christina Lim、Tan Xiang Jie、Hai-Yan Yang

  DOI：10.1002/adsc.200600361

  日期：2007.7.2

  substrates could increase the enantioselectivity. The achieved excellent enantioselectivities may be due to the corresponding substrate matches well fitting the chiral space created by the chiral palladium(II)-BINAP catalyst. The ortho-methyl substituents may improve the fitting of the substrate match to the chiral space created by the chiral catalyst, hence the enantioselectivity is improved. When using

  系统地研究了钯（II）-BINAP催化的10个芳基乙二醛和5个烯烃之间的对映选择性羰基烯反应，并显示出良好的对映体选择性，高ee值高达93.8％。结果表明，芳基乙二醛和烯烃均对对映选择性产生明显影响。特别地，底物的邻甲基取代基可以增加对映选择性。获得的优异的对映选择性可能是由于相应的底物匹配性很好地适合了由手性钯（II）-BINAP催化剂产生的手性空间。在邻-甲基取代基可以改善底物与手性催化剂产生的手性空间的匹配性，因此提高了对映选择性。当在该反应中使用二烯（1,4-二异丙烯基苯和1,3-二异丙烯基苯）作为底物时，只有两个碳-碳双键中的一个参与反应，从而提供中等官能度至多83.8％ee的四官能有机化合物。结合有（R）-BINAP的手性路易斯酸钯（II）催化剂是一种构象受限的手性配体，在离子液体中非常稳定，在保留高对映选择性的情况下可以循环使用21次。
• Enantioselective Carbonyl-Ene Reaction of Glyoxal Derivatives Catalyzed by Cationic 3-Oxobutylideneaminatocobalt(III) Complexes
  作者：Satoko Kezuka、Youichi Kogami、Taketo Ikeno、Tohru Yamada

  DOI：10.1246/bcsj.76.49

  日期：2003.1

  Optically active 3-oxobutylideneaminatocobalt(III) complexes were designed for the catalytic enantioselective carbonyl-ene reaction. Varieties of counter anions of cationic cobalt(III) complexes were screened and hexafluoroantimonate was found to be the most effective. In the presence of cobalt(III) hexafluoroantimonate complex 1f, the enantioselective carbonyl-ene reaction of various alkenes with

  光学活性 3-oxobutylideneaminatocobalt (III) 配合物被设计用于催化对映选择性羰基 - 烯反应。筛选了各种阳离子钴 (III) 配合物的抗衡阴离子，发现六氟锑酸盐是最有效的。在六氟锑酸钴 (III) 络合物 1f 的存在下，进行了各种烯烃与乙二醛衍生物的对映选择性羰基 - 烯反应，以高产率和高对映选择性得到相应的高烯丙醇。即使在 0.2 mol% 的钴 (III) 配合物存在下，反应也能以高产率进行，并保持高对映选择性。
• Optically Active β-Ketoiminato Cationic Cobalt(III) Complexes:  Efficient Catalysts for Enantioselective Carbonyl-Ene Reaction of Glyoxal Derivatives
  作者：Satoko Kezuka、Taketo Ikeno、Tohru Yamada

  DOI：10.1021/ol015980m

  日期：2001.6.1

  [see reaction]. Optically active beta-ketoiminato cationic cobalt(III) complexes were synthesized as effective Lewis acid catalysts for the enantioselective carbonyl-ene reaction. In the presence of a catalytic amount of cobalt(III) hexafluoroantimonate derived from the optically active 1,2-diphenyl-1,2-ethanediamine, the carbonyl-ene reaction with a variety of alkenes and glyoxal derivatives smoothly

  [请参阅反应]。合成了光学活性的β-酮亚氨基阳离子钴（III）配合物，作为有效的路易斯酸催化剂，用于对映选择性羰基-烯反应。在催化量的光学活性1,2-二苯基-1,2-乙二胺衍生的六氟锑酸钴（III）的存在下，羰基-烯与各种烯烃和乙二醛衍生物的反应顺利进行，得到相应的均聚物高至高收率和高对映选择性的醇。