(3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-(methoxymethoxy)methyl]-5-[(1R,2S)-2-(2-methyl-1,3-dithiolan-2-yl)-1-hydroxypropyl]tetrahydro-4H-thiopyran-4-one | 1413946-03-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: (3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-(methoxymethoxy)methyl]-5-[(1R,2S)-2-(2-methyl-1,3-dithiolan-2-yl)-1-hydroxypropyl]tetrahydro-4H-thiopyran-4-one
• 英文别名: (3R,5R)-3-[(R)-[(6S)-1,4-dioxa-8-thiaspiro[4.5]decan-6-yl]-(methoxymethoxy)methyl]-5-[(1R,2S)-1-hydroxy-2-(2-methyl-1,3-dithiolan-2-yl)propyl]thian-4-one
• CAS: 1413946-03-8
• 化学式: C₂₂H₃₆O₆S₄
• 分子量: 524.788
• InChiKey: RTDCPINIPBVRIN-RKCSFXCNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  175
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  ethyl 2-(2-methyl-1,3-dithiolan-2-yl)propanoate 在 lithium aluminium tetrahydride 、 lithium diisopropyl amide 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 6.0h， 生成 (3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-(methoxymethoxy)methyl]-5-[(1S,2R)-2-(2-methyl-1,3-dithiolan-2-yl)-1-hydroxypropyl]tetrahydro-4H-thiopyran-4-one 、 (3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-(methoxymethoxy)methyl]-5-[(1R,2S)-2-(2-methyl-1,3-dithiolan-2-yl)-1-hydroxypropyl]tetrahydro-4H-thiopyran-4-one
  参考文献：
  名称：

  Aldol Reactions with Kinetic Resolution: Scope and Limitations of Ketal- and Dithioketal-Protected β-Ketoaldehydes

  摘要：

  The multiplicativity rule suggests that aldol coupling chiral reactants will proceed with substantial mutual kinetic enantioselection (MKE) (racemic reactants) or via a highly enantioselective kinetic resolution (KR) (one enantiopure reactant) if the relative topicity is highly selective and the ketone enolate and aldehyde each have high diastereoface selectivity. The scope and limitations of that paradigm were explored by determining the stereoselectivities of aldol reactions ketone 1a (known to give 3,5-trans aldol adducts with high selectivity) with a series of ketal- and dithioketal-protected beta-ketoaldehydes (+/-)-5 (predicted to have high Felkin diastereoface selectivity). Using racemic reactants, all reactions of the (c-Hex)(2)B enolates (highly anti-selective relative topicity) were remarkably selective and gave the 3,5-trans-3,1 ''-anti-1 '',2 ''-syn adduct, one of eight possible diastereomers, via a diastereomers, via a diastereoselective (dr > 20) preferential reaction (MKE > 17) of like reactant enantiomers [i.e., (3R)-1a + (R)-5 and (3S)-1a + (S)-5]. Reactions of the corresponding Ti(IV) "ate" enolates (anticipated syn-selective relative topicity) were much less selective, and only those of MOM-protected 1a with dithiolane-protected (+/-)-5 (i.e., X = S, n = 1) gave high selectivity in favor of the 3,5-trans-3,1 ''-syn-1 '', 2 ''-syn adduct via a diastereoselective (dr > 20) preferential reaction (MKE >= 6) of unlike reactant enantiomers [i.e., (3R)-1a (R = MOM) with (+/-)-5c (R-2 = Me, X = S, n = 1) occured withKR to give the corresponding enantiopure adducrs with the expected stereoselectivity. The adducts have applications in polyproionate synthesis.

  DOI：

  10.1021/jo302142v

文献信息

• Aldol Reactions with Kinetic Resolution: Scope and Limitations of Ketal- and Dithioketal-Protected β-Ketoaldehydes
  作者：Dale E. Ward、Alieh Kazemeini

  DOI：10.1021/jo302142v

  日期：2012.12.7

  The multiplicativity rule suggests that aldol coupling chiral reactants will proceed with substantial mutual kinetic enantioselection (MKE) (racemic reactants) or via a highly enantioselective kinetic resolution (KR) (one enantiopure reactant) if the relative topicity is highly selective and the ketone enolate and aldehyde each have high diastereoface selectivity. The scope and limitations of that paradigm were explored by determining the stereoselectivities of aldol reactions ketone 1a (known to give 3,5-trans aldol adducts with high selectivity) with a series of ketal- and dithioketal-protected beta-ketoaldehydes (+/-)-5 (predicted to have high Felkin diastereoface selectivity). Using racemic reactants, all reactions of the (c-Hex)(2)B enolates (highly anti-selective relative topicity) were remarkably selective and gave the 3,5-trans-3,1 ''-anti-1 '',2 ''-syn adduct, one of eight possible diastereomers, via a diastereomers, via a diastereoselective (dr > 20) preferential reaction (MKE > 17) of like reactant enantiomers [i.e., (3R)-1a + (R)-5 and (3S)-1a + (S)-5]. Reactions of the corresponding Ti(IV) "ate" enolates (anticipated syn-selective relative topicity) were much less selective, and only those of MOM-protected 1a with dithiolane-protected (+/-)-5 (i.e., X = S, n = 1) gave high selectivity in favor of the 3,5-trans-3,1 ''-syn-1 '', 2 ''-syn adduct via a diastereoselective (dr > 20) preferential reaction (MKE >= 6) of unlike reactant enantiomers [i.e., (3R)-1a (R = MOM) with (+/-)-5c (R-2 = Me, X = S, n = 1) occured withKR to give the corresponding enantiopure adducrs with the expected stereoselectivity. The adducts have applications in polyproionate synthesis.