trans-3,4,5,6-tetrahydro-6-(hydroxymethyl)-2-methoxy-2H-pyran | 63358-57-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: trans-3,4,5,6-tetrahydro-6-(hydroxymethyl)-2-methoxy-2H-pyran
• 英文别名: trans-6-Hydroxymethyl-2-methoxytetrahydropyran；[(2R,6R)-6-methoxyoxan-2-yl]methanol
• CAS: 63358-57-6
• 化学式: C₇H₁₄O₃
• 分子量: 146.186
• InChiKey: OAOIOIJKDGYSEQ-RNFRBKRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  trans-5,6-dihydro-6-(hydroxymethyl)-2-methoxy-2H-pyran 生成 trans-3,4,5,6-tetrahydro-6-(hydroxymethyl)-2-methoxy-2H-pyran
  参考文献：
  名称：

  JURCZAK, J.;BAUER, T.;FILIPEK, S.;TKACZ, M.;ZYGO, K., J. CHEM. SOC. CHEM. COMMUN., 1983, 9, 540-542

  摘要：

  DOI：

文献信息

• Enantioselective Hetero-Diels-Alder reaction with glyoxylate catalyzed by chiral titanium complex: asymmetric synthesis of the lactone portion of mevinolin and compactin
  作者：Masahiro Terada、Koichi Mikami、Takeshi Nakai

  DOI：10.1016/s0040-4039(00)92124-5

  日期：1991.2

  Asymmetric Diels-Alder reaction with methyl glyoxylate catalyzed by the chiral titanium complex 1 provides the dihydropyran carboxylate in high enantiomeric purity, which can be converted to the lactone portion of mevinolin or compactin.

  通过手性钛络合物1催化的乙醛酸甲酯与不对称Diels-Alder反应提供了高对映体纯度的二氢吡喃羧酸盐，其可以转化为美维林或紧密蛋白的内酯部分。
• The high-pressure [4+2]cycloaddition of 1-methoxybuta-1,3-diene to the glycolaldehyde-derived heterodienophiles, catalyzed by chiral metallosalen complexes
  作者：Piotr Kwiatkowski、Wojciech Chaładaj、Małgorzata Malinowska、Monika Asztemborska、Janusz Jurczak

  DOI：10.1016/j.tetasy.2005.07.031

  日期：2005.9

  A high-pressure (ca. 10 kbar) reaction of 1-methoxybuta-1,3-diene 1 with variously O-protected glycolaldehydes 2, catalyzed by the chiral (salen)Cr(III)Cl 4a–d and 5 or (salen)Co(II) 6a–f and 7 complexes, has been studied. The best results were obtained for tert-butyldimethylsilyloxyacetaldehyde 2a. The reaction afforded, in good yield (up to 90%) and with very good diastereoselectivity (up to 92%)

  手性（salen）Cr（III）Cl 4a – d和5或（salen ）催化的1-甲氧基丁1,3-二烯1与各种O保护的乙醇醛2的高压（大约10 kbar）反应）Co（II）6a – f和7种配合物已被研究。叔丁基二甲基甲硅烷基氧基乙醛2a获得了最佳结果。该反应以[4 + 2]环加合物3a的高收率（最高90％）和非对映选择性（最高92％）和对映选择性（最高93％ee）提供。，是具有重大合成意义的化合物。讨论了环加成反应的立体化学模型。
• The enantioselective high-pressure Diels–Alder reaction of 1-methoxybuta-1,3-diene with tert-butyldimethylsilyloxyacetaldehyde catalyzed by (salen)Co(II) and (salen)Cr(III)Cl complexes
  作者：Małgorzata Malinowska、Piotr Kwiatkowski、Janusz Jurczak

  DOI：10.1016/j.tetlet.2004.08.081

  日期：2004.10

  reaction of 1-methoxybuta-1,3-diene (1) with tert-butyldimethylsilyloxyacetaldehyde (2), catalyzed by the chiral (salen)Co(II) 4 or (salen)Cr(III)Cl 5 complexes, has been studied. We found that the reaction afforded, in good yield (up to 90%) and both with very good diastereoselectivity (up to 92%) and enantioselectivity (up to 94% ee), the [4 + 2]cycloadducts 3, which are compounds of significant synthetic

  1-methoxybuta -1,3-二烯（的高压（10-11千巴）反应1）与叔-butyldimethylsilyloxyacetaldehyde（2）中，由催化手性（沙仑）钴（II）4或（沙仑）铬（ III）Cl 5配合物，已经被研究。我们发现该反应提供了[4 + 2]环加合物3，该化合物收率好（达90％），非对映选择性（达92％）和对映选择性（达94％ee）都很好。具有重要的综合意义。
• Process for producing optically active dihydropyran derivative
  申请人：Takasago International Corporation

  公开号：US05155240A1

  公开（公告）日：1992-10-13

  A process for producing an optically active dihydropyran derivative represented by formula (1): ##STR1## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 each represents a hydrogen atom, a lower alkyl group, a tri-lower alkylsilylmethyl group, a lower alkoxycarbonylamino group, or an --OR.sup.5 group, wherein R.sup.5 represents a lower alkyl group, a lower acyl group, a lower alkoxycarbonyl group, a di-lower alkylcarbamoyl group, or a tri-lower alkylsilyl group, or R.sup.1 and R.sup.2 are taken together to form a 5- to 7-membered cyclic hydrocarbon group or to form a condensed heterocyclic group with an oxygen atom, or R.sup.2 and R.sup.3 are taken together to form a 5- to 7-membered cyclic hydrocarbon group or to form a condensed heterocyclic group with an oxygen atom, provided that all of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 do not represent hydrogen atoms at the same time; and R.sup.6 represents a lower alkyl group, which comprises reacting a diene compound represented by formula (2): ##STR2## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 have the same meanings as defined above, with a glyoxylic acid ester represented by formula (3): ##STR3## wherein R.sup.6 has the same meaning as defined above, in the presence of a binaphthol-titanium complex represented by formula (4): ##STR4## wherein X represents a chlorine atom or a bromine atom, is disclosed.

  一种生产光学活性二氢吡喃衍生物的方法，其化学式为（1）：##STR1## 其中R.sup.1、R.sup.2、R.sup.3和R.sup.4分别表示氢原子、低级烷基、三低级烷基硅甲基基团、低级烷氧羰基氨基基团或--OR.sup.5基团，其中R.sup.5表示低级烷基、低级酰基、低级烷氧羰基基团、二低级烷基氨基基团或三低级烷基硅基基团，或R.sup.1和R.sup.2结合形成5-至7-成员环烃基团或与氧原子形成紧缩杂环基团，或R.sup.2和R.sup.3结合形成5-至7-成员环烃基团或与氧原子形成紧缩杂环基团，前提是所有R.sup.1、R.sup.2、R.sup.3和R.sup.4不同时表示氢原子；且R.sup.6表示低级烷基。该方法包括在存在双萘酚钛配合物（化学式（4））的情况下，将化学式（2）所表示的二烯化合物与化学式（3）所表示的甘酸酯反应，其中R.sup.1、R.sup.2、R.sup.3和R.sup.4的含义如上所定义，R.sup.6的含义如上所定义，X表示氯原子或溴原子。
• Asymmetric Catalysis of Diels-Alder Cycloadditions by an MS-Free Binaphthol-Titanium Complex: Dramatic Effect of MS, Linear vs Positive Nonlinear Relationship, and Synthetic Applications
  作者：Koichi Mikami、Yukihiro Motoyama、Masahiro Terada

  DOI：10.1021/ja00086a014

  日期：1994.4

  Asymmetric Diels-Alder (D.-A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the endo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at -20 degrees C, Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.-A. cycloaddition of methacrolein and glyoxylate with 1,3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (R)-1 with (S)-1 or (+/-)-1.