(S)-(-)-Ethyl 4,5-dimethyl-3,6-dihydro-2H-pyran-2-carboxylate | 172323-53-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (S)-(-)-Ethyl 4,5-dimethyl-3,6-dihydro-2H-pyran-2-carboxylate
• 英文别名: (S)-4,5-Dimethyl 3,6-dihydro-2H-pyran-2-carboxylic acid ethyl ester；ethyl (2S)-4,5-dimethyl-3,6-dihydro-2H-pyran-2-carboxylate
• CAS: 172323-53-4
• 化学式: C₁₀H₁₆O₃
• 分子量: 184.235
• InChiKey: AIODUTCADHYBDL-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  乙醛酸乙酯 、 2,3-二甲基-1,3-丁二烯 在 an chiral bisoxazoline 、 zinc trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 反应 50.0h， 生成 ethyl 2-hydroxy-5-methyl-4-methylidenehex-5-enoate 、 (R)-(+)-Ethyl 4,5-dimethyl-3,6-dihydro-2H-pyran-2-carboxylate 、 (S)-(-)-Ethyl 4,5-dimethyl-3,6-dihydro-2H-pyran-2-carboxylate
  参考文献：
  名称：

  Zinc(II)-catalysed asymmetric hetero-Diels–Alder reactions of conjugated dienes with glyoxylate

  摘要：

  在不同的 C2 对称双噁唑啉存在下，研究了锌(II)催化的共轭二烯 2,3-二甲基丁-1,3-二烯和环己-1,3-二烯与乙醛酸乙酯的杂 DielsâAlder 反应。 锌（II）催化的 2,3-二甲基丁-1,3-二烯与乙醛酸乙酯的反应产生了杂-DielsâAlder 和烯产物，前者是主要产物，对映体过量率高达 87%。杂-DielsâAlderâceene 的比例与催化体系和溶剂相对无关，范围在 1â¶0.5â1â¶0.8。锌（II）催化的环己-1,3-二烯与乙醛酸乙酯的反应中，杂-DielsâAlder 生成物的分离收率高达 84%，对映体过量率高达 65%。该反应的对映体过量与溶剂有很大关系，与 CH2Cl2 相比，MeNO2 通常会降低对映体过量。根据杂-DielsâAlder 产物的绝对立体化学性质以及对不同双噁唑啉锌(II)-乙醛酸乙酯中间体的半经验计算，讨论了该反应的机理。

  DOI：

  10.1039/a701882g

文献信息

• Zinc(II)-catalysed asymmetric hetero-Diels–Alder reactions of conjugated dienes with glyoxylate
  作者：Sulan Yao、Mogens Johannsen、Karl Anker Jørgensen

  DOI：10.1039/a701882g

  日期：——

  The zinc(II)-catalysed hetero-Diels–Alder reaction of the conjugated dienes 2,3-dimethylbuta-1,3-diene and cyclohexa-1,3-diene with ethyl glyoxylate has been studied in the presence of different C2-symmetric bisoxazolines. The zinc(II)-catalysed reaction of 2,3-dimethylbuta-1,3-diene with ethyl glyoxylate gives both the hetero-Diels–Alder and ene products, the former being the major product with an enantiomeric excess up to 87%. The hetero-Diels–Alder∶ene ratio is relatively independent of the catalytic system and the solvent and is in the range 1∶0.5–1∶0.8. For the zinc(II)-catalysed reaction of cyclohexa-1,3-diene with ethyl glyoxylate, the hetero-Diels–Alder product is formed in up to 84% isolated yield and with an enantiomeric excess up to 65%. The enantiomeric excess for this reaction is very dependent on the solvent, with MeNO2 generally lowering the enantiomeric excess compared with CH2Cl2. Based on the absolute stereochemistry of the hetero-Diels–Alder products and semi-empirical calculations on different bisoxazoline–zinc(II)–ethyl glyoxylate intermediates the mechanism for the reaction is discussed.

  在不同的 C2 对称双噁唑啉存在下，研究了锌(II)催化的共轭二烯 2,3-二甲基丁-1,3-二烯和环己-1,3-二烯与乙醛酸乙酯的杂 DielsâAlder 反应。 锌（II）催化的 2,3-二甲基丁-1,3-二烯与乙醛酸乙酯的反应产生了杂-DielsâAlder 和烯产物，前者是主要产物，对映体过量率高达 87%。杂-DielsâAlderâceene 的比例与催化体系和溶剂相对无关，范围在 1â¶0.5â1â¶0.8。锌（II）催化的环己-1,3-二烯与乙醛酸乙酯的反应中，杂-DielsâAlder 生成物的分离收率高达 84%，对映体过量率高达 65%。该反应的对映体过量与溶剂有很大关系，与 CH2Cl2 相比，MeNO2 通常会降低对映体过量。根据杂-DielsâAlder 产物的绝对立体化学性质以及对不同双噁唑啉锌(II)-乙醛酸乙酯中间体的半经验计算，讨论了该反应的机理。
• A highly chemo- and enantio-selective hetero-Diels–Alder reaction catalysed by chiral aluminium complexes
  作者：Anette Graven、Mogens Johannsen、Karl Anker Jørgensen

  DOI：10.1039/cc9960002373

  日期：——

  A new, highly chemo- and enantio-selective catalytic hetero Diels-Alder reaction of conjugated dienes containing allylic C-H bonds with carbonyl compounds has been developed; with the use of (S)-(-)-BINOL-AlMe (BINOL = 1,1'-bi-2-naphthol) as a catalyst, simple conjugated dienes react with glyoxylate esters, giving the (R)-enantiomer of the hetero-Diels-Alder adduct as the major product with up to 97% ee.
• Asymmetric Hetero Diels−Alder Reaction Catalyzed by Chiral Cationic Palladium(II) and Platinum(II) Complexes
  作者：Shuichi Oi、Eiji Terada、Kazuei Ohuchi、Tomoko Kato、Yukari Tachibana、Yoshio Inoue

  DOI：10.1021/jo9906680

  日期：1999.11.1

  The hetero Diels-Alder reaction of nonactivated conjugated dienes 1 with arylglyoxals 2 and glyoxylate esters 7 proceeded enantioselectively in the presence of a catalytic amount of cationic chiral BINAP-palladium or -platinum complexes and 3 Angstrom molecular sieves (MS3A). The addition of MS3A effectively improved the enantioselectivity of the reaction. Excellent ee's were obtained from the reactions of 2,3-dimethyl-1,3-butadiene (1a) and 1,3-cyclohexadiene (1d) with dienophiles 2 and 7. The square-planar structure of [Pd(S-BINAP)(PhCN)(2)](PF6)(2) was determined by X-ray diffraction, and a chiral induction model involving the square-planar palladium complex coordinated with BINAP and a dienophile is proposed.
• Asymmetric hetero Diels-Alder reactions and ene reactions catalyzed by chiral copper(II) complexes
  作者：Mogens Johannsen、Karl Anker Joergensen

  DOI：10.1021/jo00123a007

  日期：1995.9

  A new copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes leading to the hetero Diet-Alder product and the ene product in high yield and with a high enantiomeric excess (ee) has been developed. The hetero Diels-Alder product:ene product ratio is in the range 1:0.6 to 1:1.8 and is dependent on both the chiral ligand attached to the metal, the glyoxylate ester, and the reaction temperature. The scope of the copper(II) bisoxazoline-catalyzed reaction of glyoxylate esters with dienes is demonstrated by the reaction of a variety of different dienes with ethyl and isopropyl glyoxylate, and it is shown that a simple substrate such as 1,3-butadiene reacts to give the hetero Diels-Alder product in 55% yield with an ee of 87%. Furthermore, the synthetic application of the reaction is demonstrated by the synthesis of a highly interesting synthon for sesquiterpene lactones in high yield and diastereoselectivity, and with a very high ee from 1,3-cyclohexadiene and ethyl glyoxylate using a copper(II) bisoxazoline as the catalyst. A mechanism for the hetero Diels-Alder reaction, which accounts for the enantioselectivity in the reactions, is proposed.
• A Highly Enantioselective Hetero-Diels−Alder Reaction Catalyzed by Chiral Polybinaphthyl−Aluminum Complexes
  作者：Mogens Johannsen、Karl Anker Jørgensen、Xiao-Fan Zheng、Qiao-Sheng Hu、Lin Pu

  DOI：10.1021/jo981466r

  日期：1999.1.1