(2S,6S)-2-[(benzyloxy)methyl]-6-methoxy-3,6-dihydro-2H-pyran | 130857-02-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,6S)-2-[(benzyloxy)methyl]-6-methoxy-3,6-dihydro-2H-pyran
• 英文别名: trans-6-((benzyloxy)methyl)-5,6-dihydro-2-methoxy-2H-pyran；(2S)-methoxy-(6S)-benzyloxymethyl-5,6-dihydro-2H-pyran；(2S,6S)-6-methoxy-2-(phenylmethoxymethyl)-3,6-dihydro-2H-pyran
• CAS: 130857-02-2
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: DGIDIHDKOKZGLX-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,6S)-2-[(benzyloxy)methyl]-6-methoxy-3,6-dihydro-2H-pyran 生成 (2S,6S)-4,6-dimethoxy-2-(phenylmethoxymethyl)-3,6-dihydro-2H-pyran
  参考文献：
  名称：

  BANASZEK, ANNA, BULL. POL. ACAD. SCI. CHEM., 36,(1988) N-6, C. 277-283

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-苄氧甲基环氧乙烷 在 吡啶 、 titanium(IV) isopropylate 、 三氟甲磺酸三甲基硅酯 、 TEA 、 镍 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 7.08h， 生成 (2S,6S)-2-[(benzyloxy)methyl]-6-methoxy-3,6-dihydro-2H-pyran
  参考文献：
  名称：

  Synthesis of 4-Deoxy-l-(and d-)hexoses from Chiral Noncarbohydrate Building Blocks

  摘要：

  4-Deoxy-L-hexoses were synthesized starting from our previously reported reagent 1 and (R)-benzyl glycidyl ether, which led in few steps to a substituted dihydropyran 6. The stereocontrolled hydroxylation of the latter afforded the corresponding 4-deoxy-L-hexoses 7a, 9, and 11. The same procedure, starting from (S)-benzyl glycidyl ether, enabled the preparation of their D-series enantiomers.

  DOI：

  10.1021/jo0493774

文献信息

• 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。
• Stereochemical course of the [4+2] cycloaddition of 1-methoxybuta-1,3-diene to N-glyoxyloyl-(2R)-bornane-10,2-sultam. The formal synthesis of compactin and mevinolin
  作者：Tomasz Bauer、Christian Chapuis、Artur Jez̀ewski、Janusz Kozak、Janusz Jurczak

  DOI：10.1016/0957-4166(96)00156-5

  日期：1996.5

  ne-10,2-sultam 2, readily prepared from (2R)-bornane-10,2-sultam 1, was used in noncatalyzed atmospheric and high-pressure as well as in [Eu(fod)3]-catalyzed [4+2] cycloadditions with 1-methoxybuta-1,3-diene 3. All the [4+2] cycloadditions studied led to diastereoisomeric mixtures of 6-substituted derivatives of 2-methoxy-5,6-dihydro-2H-pyran 4–7. The extent of asymmetric induction in these reactions

  手性heterodienophile Ñ -glyoxyloyl-（2 - [R）-bornane-10,2-磺内酰胺2，容易从（2制备- [R）-bornane-10,2-磺内酰胺1，在非催化常压和高压用以及在[Eu（fod）3 ]催化的1-4-甲氧基-1,3-二烯3的[4 + 2]环加成反应中。所有研究的[4 + 2]环加成反应均导致2-甲氧基-5,6-二氢-2H-吡喃4-7的6-取代衍生物的非对映异构体混合物。通过1 H NMR分析和热力学稳定产物5和7的绝对构型，确定了这些反应中的不对称诱导程度。通过X射线分析，并通过化学相关独立进行。提出了针对非催化和[Eu（fod）3 ]促进的反应的立体化学模型。然后将[4 + 2]环加合物5有效地转化为（4 R）-羟基-（6S）-羟甲基四氢吡喃酮2 12，这是Compactin 10和mevinolin 11内酯部分的关键合成子。
• Diastereoselective synthesis of the lactone portion of compactin and mevinolin
  作者：Tomasz Bauer、Janusz Kozak、Christian Chapuis、Janusz Jurczak

  DOI：10.1039/c39900001178

  日期：——

  The highly diastereoselective [4 + 2] cycloaddition of 1-methoxybuta-1,3-diene (3) to (2R)-N-glyoxyloylbornane-10,2-sultam (2) afforded the adduct (4) which was effectively transformed into (4R,6S)-4-hydroxy-6-hydroxymethyltetrahydro-2-pyrone (1), a key synthon for the lactone moiety of compactin and mevinolin.

  将1-甲氧基丁1,3-二烯（3）高度非对映选择性的[4 + 2]环加成（2 R）-N-乙氧基乙酰冰片烷10,2-磺酰胺（2）提供加合物（4），该加合物可以有效地转化进入（4 R，6 S）-4-羟基-6-羟甲基四氢-2-吡喃酮（1），这是紧缩蛋白和美维林的内酯部分的关键合成子。
• 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.
• BAUER, TOMASZ;KOZAK, JANUSZ;CHAPUIS, CHRISTIAN;JURCZAK, JANUSZ, J. CHEM. SOC. CHEM. COMMUN.,(1990) N7, C. 1178-1179
  作者：BAUER, TOMASZ、KOZAK, JANUSZ、CHAPUIS, CHRISTIAN、JURCZAK, JANUSZ

  DOI：——

  日期：——