(+/-)-(3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(methoxymethoxy)methyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]tetrahydro-4H-thiopyran-4-one | 1160558-86-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-(3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(methoxymethoxy)methyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]tetrahydro-4H-thiopyran-4-one
• 英文别名: (+/-)-(3S,5S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-ylhydroxymethyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(methoxymethoxy)methyl]tetrahydro-4H-thiopyran-4-one；rac-(3S,5S)-3-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(methoxymethoxy)methyl]-5-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one；(3S,5S)-3-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(methoxymethoxy)methyl]-5-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one
• CAS: 1160558-86-0
• 化学式: C₂₃H₃₆O₈S₃
• 分子量: 536.732
• InChiKey: TVJGLGRCNYUTCR-GNFBJIGASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.88
• 重原子数：
  34.0
• 可旋转键数：
  7.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  92.68
• 氢给体数：
  1.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  (+/-)-(3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(methoxymethoxy)methyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]tetrahydro-4H-thiopyran-4-one 在 Raney Ni 作用下， 以 乙醇 为溶剂， 反应 1.0h， 生成 rel-(2S,3R,4R,6R,7S,8R)-2,8-bis(2-ethyl-1,3-dioxolan-2-yl)-7-hydroxy-3-methoxymethoxy-4,6-dimethylnonan-5-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
• 作为产物：
  描述：

  (+/-)-(3R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one 在 Ti(OiPr)Cl3 、 四丁基碘化铵 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 79.53h， 生成 (+/-)-(3R,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(methoxymethoxy)methyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]tetrahydro-4H-thiopyran-4-one
  参考文献：
  名称：

  硫吡喃路线向聚丙烯酸酯：利用和克服手性片段的醇醛联结中的双重立体扩散和相互动力学对映体。

  摘要：

  四氢-4 H-硫代吡喃酮与1,4-二氧杂-8-硫杂螺[4.5]癸烷-6-甲醛的醛醇缩合反应（Ⅰ）给出了四种可能的非对映异构体加合物（Ⅱ）。的羟醛缩合反应我与每个非对映体II和它们相应的甲氧基甲基醚III经由烯醇化物的Ti进行了调查。使用外消旋反应物，与II的反应以高水平的相互动力学对映异构体（MKE）和双立体分化（DS）进行，从而得到八种可能的双缩醛加合物之一。III的类似反应继续用低水平的MKE和DS进行合成，得到两个比沙多醇加合物，每个对映体反应物的可能组合中的一个。通过扩展，可以有选择地获得比沙尔多加合物的20种可能的非对映异构体中的11种。这些加合物可用于聚丙烯酸酯的合成。

  DOI：

  10.1021/jo0622532

文献信息

• Rational Design of Aldol Reactions That Proceed via Kinetic Resolution with Switchable Enantioselectivity
  作者：Dale E. Ward、Fabiola Becerril-Jimenez、M. Mehdi Zahedi

  DOI：10.1021/jo900716a

  日期：2009.6.19

  hydroxy-protected derivatives of ketone 1 (R = MOM, Et3Si, or Ac) undergo aldol reactions with high diastereoface selectivity to give 3,5-trans adducts. High levels of anti and syn relative topicity were obtained with dicyclohexylboron enolates and Ti(OiPr)4Li “ate” enolates, respectively. Using these enolates, aldol reactions of (±)-2 with (±)-1 gave two of the eight possible diastereomeric adducts (3 from

  手性反应物的醛醇缩合反应的立体选择性可以分解为三个立体控制元素：酮烯醇和醛的非对映体选择性以及偶联的相对局部性。将乘法规则应用于这些元素会导致以下预测：如果所有三个立体声控制元素都受到强烈偏置，则动力学分辨率（KR）应该是可能的。因此，动力学分辨率的对映选择性应可通过改变任何立体控制元件的选择性来切换。使用具有高非对映选择性的醛和酮反应物并开发了强烈支持顺式或反式相对位置性的反应条件，对这一假设进行了测试。醛2进行具有几乎排他的Felkin非对映体选择性的醛醇缩合反应，酮1的羟基保护衍生物（R = MOM，Et 3 Si或Ac）进行非对映体选择性高的醛醇缩合反应，得到3,5-反式加合物。的高水平的抗和顺式与钛（O dicyclohexylboron烯醇化物并得到相对topicity我PR）4分别李“吃”烯醇化物。使用这些烯醇化物，（±）-2与（±）-1的醛醇缩合反应可得到八种可能的非对映异
• Syn−Anti Isomerization of Aldols by Enolization
  作者：Dale E. Ward、Marcelo Sales、Pradip K. Sasmal

  DOI：10.1021/jo049626o

  日期：2004.7.1

  structurally related aldols derived from cyclohexanone isomerized ca. 3−4 times slower. Isomerization of the acyclic aldol 5-hydroxy-4-methyl-5-phenyl-3-pentanone required heating to 60 °C but was achieved with minimal (<5%) retroaldol or elimination. A methoxymethyl ether derivative isomerized 30−40 times slower than the parent aldol. Isomerization of α,α‘-disubstituted aldols and α,α‘-bisaldols indicated

  在咪唑存在下，通过烯醇化机理，各种羟醛加合物均表现出有效的顺反异构化。异构化是高收率的，并且很少发生或几乎没有由竞争性消除或逆醛醇缩合反应产生的常见副产物。大多数底物在环境温度下于0.3-3天内在含有0.3-1 M咪唑的氯仿，苯或二氯甲烷中达到平衡。该方法对于衍生自四氢-4 H的羟醛特别容易-硫吡喃-4-酮的平衡速率常数随时间的变化而变化。研究的加合物的数量级为1个数量级；结构相关的羟醛衍生自环己酮异构化约。慢3-4倍。无环羟醛5-羟-4-甲基-5-甲基-5-苯基-3-戊酮的异构化需要加热至60°C，但只需极少（<5％）逆醛醇或消除即可。甲氧基甲基醚衍生物的异构化速度比母体醛醇慢30-40倍。α，α′-二取代的醛醇和α，α′-二醛醇的异构化表明烯醇化中的区域选择性低。有效制备通过直接方法无法获得的羟醛立体异构体证明了该方法的合成效用。