methyl (3R,5R)-3,5-dihydroxyhexanoate | 115461-00-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl (3R,5R)-3,5-dihydroxyhexanoate
• 英文别名: methyl (3R,5R)-syn-3,5-hydroxyhexanoate；methyl (3R,5R)-dihydroxyhexanoate
• CAS: 115461-00-2
• 化学式: C₇H₁₄O₄
• 分子量: 162.186
• InChiKey: AYPJVPWNLGHTEP-PHDIDXHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (3R,5R)-3,5-dihydroxyhexanoate 在 4 A molecular sieve 、 zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以83%的产率得到(4R,6R)-4-羟基-6-甲基四氢-2H-吡喃-2-酮
  参考文献：
  名称：

  Enantioselective Synthesis of the Unsymmetrical Bis(lactone) (−)-(3E,6R,9E,12S,14R)-Colletol Induced by Chiral Sulfoxides and an Approach to (+)-Colletodiol by Asymmetric Hydroxylation of an α,β-Hydroxy Lactone

  摘要：

  A general synthetic strategy towards the two bis(lactones) (-)-colletol (1) and (+)-colletodiol (2) is described. A common intermediate in this synthesis is the 6-membered hydroxy lactone (+)-(3R,SR)-3-hydroxy-5-hexanolide (6), readily prepared by stereoselective reduction of (+)-(SR)-methyl 3,5-dioxo -6-(p-toluenesulfinyl)hexanoate (7). Stereoselective hydroxylation of this hydroxy lactone has allowed efficient access to (+)-colletodiol(2).

  DOI：

  10.1002/(sici)1099-0690(200001)2000:2<357::aid-ejoc357>3.0.co;2-n
• 作为产物：
  描述：

  3,5-二酮己酸甲酯 在 二乙基甲氧基硼烷 、 叔丁基锂 、 镍 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 、 正戊烷 为溶剂， 反应 14.25h， 生成 methyl (3R,5R)-3,5-dihydroxyhexanoate
  参考文献：
  名称：

  Enantioselective Synthesis of the Unsymmetrical Bis(lactone) (−)-(3E,6R,9E,12S,14R)-Colletol Induced by Chiral Sulfoxides and an Approach to (+)-Colletodiol by Asymmetric Hydroxylation of an α,β-Hydroxy Lactone

  摘要：

  A general synthetic strategy towards the two bis(lactones) (-)-colletol (1) and (+)-colletodiol (2) is described. A common intermediate in this synthesis is the 6-membered hydroxy lactone (+)-(3R,SR)-3-hydroxy-5-hexanolide (6), readily prepared by stereoselective reduction of (+)-(SR)-methyl 3,5-dioxo -6-(p-toluenesulfinyl)hexanoate (7). Stereoselective hydroxylation of this hydroxy lactone has allowed efficient access to (+)-colletodiol(2).

  DOI：

  10.1002/(sici)1099-0690(200001)2000:2<357::aid-ejoc357>3.0.co;2-n

文献信息

• Tuning diastereoselectivity with the solvent: the asymmetric hydrogenation of simple and functionalized 1,3-diketones with ruthenium(amidophosphine–phosphinite) catalysts
  作者：Ve´ronique Blandin、Jean-François Carpentier、Andre´ Mortreux

  DOI：10.1039/b000962h

  日期：——

  Spectacular solvent effects in the asymmetric hydrogenation of methyl 3,5-dioxohexanoate (3) and 2,4-pentanedione (5) have been observed using Ru[(S)-Ph,Ph-oxoProNOP]X2 complexes (X=η3-C4H7, IIa; CF3CO2, IIb; (R)-MTPA, IIc) as catalyst precursors. β-Diketones 3 and 5 are respectively reduced to the corresponding β-diols 4 and 6. In both cases, an almost complete reversal in the diastereoselectivity of the reaction is observed when changing the solvent from CH2Cl2 (syn-4 in up to 92% de; meso-6 in up to 84% de) to a 1:1 CH2Cl2–CH3OH mixture (anti-4 and anti-6 in up to 84% de). The extent of this solvent effect is much less marked with Ru-atropisomeric diphosphine catalysts.

  使用Ru[(S)-Ph,Ph-oxoProNOP]X2（X=η3-C4H7，IIa；CF3CO2，IIb；（R）-MTPA，IIc）作为催化剂前体，在甲基3,5-二氧代己酸（3）和2,4-戊二酮（5）的不对称氢化反应中观察到了壮观的光学溶剂效应。β-二酮3和5分别被还原为相应的β-二醇4和6。在这两种情况下，当将溶剂从CH2Cl2（顺式-4的脱除率高达92%；中式-6的脱除率高达84%）变为1:1的 -CH3OH混合物（反式-4和反式-6的脱除率高达84%）时，反应的立体选择性几乎完全相反。Ru-对映异构体二膦催化剂的溶剂效应程度要小得多。
• Mahler, Ulrike; Devant, Ralf M.; Braun, Manfred, Chemische Berichte, 1988, vol. 121, p. 2035 - 2044
  作者：Mahler, Ulrike、Devant, Ralf M.、Braun, Manfred

  DOI：——

  日期：——
• One-Pot and Sequential Asymmetric Hydrogenation of β,δ-Diketoesters into Functionalized 1,3-Diols: Fromanti- tosyn-Stereoselectivity
  作者：Véronique Blandin、Jean-François Carpentier、André Mortreux

  DOI：10.1002/(sici)1099-0690(199912)1999:12<3421::aid-ejoc3421>3.0.co;2-1

  日期：1999.12
• MAHLER, ULRIKE;DEVANT, RALF M.;BRAUN, MANFRED, CHEM. BER., 121,(1988) N 11, C. 2035-2044
  作者：MAHLER, ULRIKE、DEVANT, RALF M.、BRAUN, MANFRED

  DOI：——

  日期：——