(+/-)-(3R,5S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]-5-[(S)-(6R)-1,4-dioxaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one | 381687-50-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-(3R,5S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]-5-[(S)-(6R)-1,4-dioxaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one
• 英文别名: (3R,5S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]tetrahydro-4H-thiopyran-4-one；(3S,5R)-5-[(R)-[(6S)-1,4-dioxa-8-thiaspiro[4.5]decan-6-yl]-hydroxymethyl]-3-[(S)-[(6R)-1,4-dioxa-8-thiaspiro[4.5]decan-6-yl]-hydroxymethyl]thian-4-one
• CAS: 381687-50-9
• 化学式: C₂₁H₃₂O₇S₃
• 分子量: 492.679
• InChiKey: YTJQGPLLEIEQTR-DVSXHRITSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  31
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  170
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (+/-)-(3R,5S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]-5-[(S)-(6R)-1,4-dioxaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  Thiopyran Route to Polypropionates:  Aldol Diastereoselectivity of Linear and Two-Directional Iterative Homologations

  摘要：

  Aldol reaction of tetrahydro-4H-thiopyran-4-one with racemic 1,4-dioxa-8-thiaspiro[4.5]decane-6-carboxaldehyde is easily controlled to give the 2,3-anti-3,4-syn or the 2,3-syn-3,4-syn adduct. Aldol homologations of these beta-hydroxy ketones with the same aldehyde occur with considerable mutual kinetic enantioselection (MKE) and, in each case, selectively give one of the eight possible diastereomers. Similar reactions of related beta-methoxy ketones are also very diastereoselective but proceed without significant MKE, resulting in two diastereomers. The adducts can be used for polypropionate synthesis.

  DOI：

  10.1021/ol005790w
• 作为产物：
  描述：

  (+/-)-(3S,5S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl-hydroxymethyl]tetrahydro-4H-thiopyran-4-one 在 咪唑 作用下， 以 氘代氯仿 为溶剂， 反应 200.0h， 生成 (+/-)-(3S,5R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]-5-[(S)-(6R)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one 、 (+/-)-(3R,5S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]-5-[(S)-(6R)-1,4-dioxaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one
  参考文献：
  名称：

  通过烯醇化对羟醛进行顺反异构化

  摘要：

  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。

  DOI：

  10.1021/jo049626o

文献信息

• Syn−Anti Isomerization of Aldols by Enolization
  作者：Dale E. Ward、Marcelo Sales、Pradip K. Sasmal

  DOI：10.1021/ol016581u

  日期：2001.11.1

  [reaction--see text] A variety of aldol adducts (i.e., 3-hydroxy ketones) are shown to undergo syn-anti isomerization in the presence of imidazole by an enolization mechanism with negligible retroaldol or elimination products.

  [反应-见正文]各种醛醇加合物（即3-羟基酮）在咪唑存在下，通过烯醇化机理与逆向醇醛或消除产物的合成反应，经历了顺反异构化。
• Thiopyran Route to Polypropionates:  Exploiting and Overcoming Double Stereodifferentiation and Mutual Kinetic Enantioselection in Aldol Couplings of Chiral Fragments
  作者：Dale E. Ward、Garrison E. Beye、Marcelo Sales、Idralyn Q. Alarcon、H. Martin Gillis、Vishal Jheengut

  DOI：10.1021/jo0622532

  日期：2007.3.1

  The aldol reaction of tetrahydro-4H-thiopyranone with 1,4-dioxa-8-thiaspiro[4.5]decane-6-carboxaldehyde (I) gives four possible diastereomeric adducts (II). Aldol reactions of I with each of the diastereomers of II and their corresponding methoxymethyl ethers III via the Ti enolates were investigated. Using racemic reactants, reactions with II proceeded with high levels of mutual kinetic enantioselection

  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。
• The Thiopyran Route to Polypropionates:  Enantioselective Synthesis of Membrenone B from Racemic Fragments
  作者：Vishal Jheengut、Dale E. Ward

  DOI：10.1021/jo701546f

  日期：2007.9.1

  [GRAPHICS](6S,7S,8S,9R,10S)-(-)-Membrenone B was synthesized in nine steps (9.4% overall yield) beginning with two-directional aldol coupling of tetrahydro-4H-thiopyran-4-one with racemic 1,4-dioxa-8-thiaspiro[4.5]decane-6-carboxaldehyde. The first aldol reaction occurs with dynamic kinetic resolution to give a single adduct (>98% ee). The second aldol reaction is highly diastereoselective (three of eight possible adducts), and both major products are converted to membrenone B. The route also constitutes a formal synthesis of membrenone A.
• Thiopyran Route to Polypropionates:  Aldol Diastereoselectivity of Linear and Two-Directional Iterative Homologations
  作者：Dale E. Ward、Cheng Guo、Pradip K. Sasmal、Chuk C. Man、Marcelo Sales

  DOI：10.1021/ol005790w

  日期：2000.5.1

  Aldol reaction of tetrahydro-4H-thiopyran-4-one with racemic 1,4-dioxa-8-thiaspiro[4.5]decane-6-carboxaldehyde is easily controlled to give the 2,3-anti-3,4-syn or the 2,3-syn-3,4-syn adduct. Aldol homologations of these beta-hydroxy ketones with the same aldehyde occur with considerable mutual kinetic enantioselection (MKE) and, in each case, selectively give one of the eight possible diastereomers. Similar reactions of related beta-methoxy ketones are also very diastereoselective but proceed without significant MKE, resulting in two diastereomers. The adducts can be used for polypropionate synthesis.