(3R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one | 916499-21-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one
• 英文别名: (3R)-3-[(R)-[(6S)-1,4-dioxa-8-thiaspiro[4.5]decan-6-yl]-hydroxymethyl]thian-4-one
• CAS: 916499-21-3
• 化学式: C₁₃H₂₀O₄S₂
• 分子量: 304.431
• InChiKey: BCKIAWGIFHKTDK-JBLDHEPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  106
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one 在 L-脯氨酸 作用下， 以 氘代二甲亚砜 、 水 为溶剂， 生成 (+/-)-(3S)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one
  参考文献：
  名称：

  具有对映体选择性和动态动力学拆分的对映选择性直接分子间羟醛反应。

  摘要：

  [反应：见正文]四氢-4H-吡喃酮与外消旋1,4-二氧杂-8-硫杂螺[4.5]癸烷-6-甲醛和内消旋/ dl 1,4-二氧杂-8的脯氨酸催化的羟醛反应-thiaspiro [4.5] decane-6,10-dibarboxaldehyde可进行动态动力学拆分，并以良好的ee收率获得高收率的单加合物。高对映体基团选择性是由于醛的高固有非对映异构体选择性所致。这些反应显着扩展了对映选择性直接醛醇缩合反应的范围，并且构成有用的四丙酸酯合成子的简单而有效的合成。

  DOI：

  10.1021/ol050195l
• 作为产物：
  描述：

  1,4-dioxa-8-thiaspiro<4.5>decane-6-carboxaldehyde 在 水 、 silica gel 、 三乙胺 、 (S)-5-(吡咯烷-2-基)-1H-四唑 作用下， 以 二甲基亚砜 、 乙酸乙酯 为溶剂， 反应 192.0h， 生成 (3R)-3-[(R)-(6S)-1,4-dioxa-8-thiaspiro[4.5]dec-6-yl(hydroxy)methyl]tetrahydro-4H-thiopyran-4-one
  参考文献：
  名称：

  Thiopyran Route to Polypropionates:  An Efficient Synthesis of Serricornin

  摘要：

  The synthesis of serricornin [(4S, 6S, 7S)-7-hydroxy-4,6-dimethylnonan- 3-one], a sex pheromone produced by the female cigarette beetle (Lasioderma serricorne F.), in seven steps from readily available racemic 1,4-dioxa-8- thiaspiro-[4.5] decane-6-carboxaldehyde (6) is described. The key steps include enantioselective aldol reaction of 6 with tetrahydrothiopyran-4- one catalyzed by 5-[(2S)-pyrrolidine-2-yl]-1H- tetrazole to fabricate the tetrapropionate skeleton, stereoselective (LiBu3BH)-Bu-s reduction of the resulting aldol adduct, Barton-McCombie deoxygenation, and Raney nickel desulfurization.

  DOI：

  10.1021/jo061747w

文献信息

• 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。
• Total Synthesis of Muamvatin
  作者：Dale E. Ward、M. Mehdi Zahedi

  DOI：10.1021/ol303004k

  日期：2012.12.21

  tautomerization of an acyclic derivative assembled by sequential substrate-controlled stereoselective aldol reactions of a chiral ketone with two achiral aldehydes. Although the trioxaadamantane tautomer was shown to be thermodynamically more stable than alternative forms, the kinetic barrier to cyclization was significant. This observation raises doubts about the proposed formation of muamvatin as an

  muamvatin的对映选择性全合成是通过无环衍生物的环链互变异构而实现的，该无环衍生物是由手性酮与两个非手性醛的连续底物控制的立体选择性醛醇缩合反应组装而成的。尽管显示三恶金刚烷互变异构体在热力学上比替代形式更稳定，但是环化的动力学障碍是显着的。这一观察结果使人们怀疑拟定形成的muamvatin是一种分离产物。
• 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.
• The thiopyran route to polypropionates. Asymmetric synthesis of the building blocks by enantioselective protonation
  作者：Dale E. Ward、Olukayode T. Akinnusi、Idralyn Q. Alarcon、Vishal Jheengut、Jianheng Shen、J. Wilson Quail

  DOI：10.1016/j.tetasy.2004.06.027

  日期：2004.8

  Enantioselective protonation of the s-BuLi derived lithium enolate of (S)-phenyl 1,4-dioxa-8-thia-spiro[4.5]decane-6-carbothioate 14 with N-isopropylephedrine 15 gives 14 as a 10:1 mixture of enantiomers. Recrystallization of nonracemic 14 gives a highly enantioenriched material (>90% ee), which can be converted into 1,4-dioxa-8-thia-spiro[4.5]decane-6-carboxaldehyde 2 without racemization. Diastereoselective aldol reactions of tetrahydro-4H-thiopyran-4-one with nonracemic 2 proceed with negligible racemization to give adducts that are useful building blocks for polypropionate synthesis. (C) 2004 Elsevier Ltd. All rights reserved.
• Enantioselective Direct Intermolecular Aldol Reactions with Enantiotopic Group Selectivity and Dynamic Kinetic Resolution
  作者：Dale E. Ward、Vishal Jheengut、Olukayode T. Akinnusi

  DOI：10.1021/ol050195l

  日期：2005.3.1

  4-dioxa-8-thiaspiro[4.5]decane-6,10-dicarboxaldehyde proceed with dynamic kinetic resolution and give single adducts in good yields with excellent ee's. The high enantiotopic group selectivity results from the high intrinsic diastereoface selectivity of the aldehydes. These reactions significantly extend the scope of the enantioselective direct aldol reaction and constitute simple and efficient syntheses of

  [反应：见正文]四氢-4H-吡喃酮与外消旋1,4-二氧杂-8-硫杂螺[4.5]癸烷-6-甲醛和内消旋/ dl 1,4-二氧杂-8的脯氨酸催化的羟醛反应-thiaspiro [4.5] decane-6,10-dibarboxaldehyde可进行动态动力学拆分，并以良好的ee收率获得高收率的单加合物。高对映体基团选择性是由于醛的高固有非对映异构体选择性所致。这些反应显着扩展了对映选择性直接醛醇缩合反应的范围，并且构成有用的四丙酸酯合成子的简单而有效的合成。