(3aS,4R,6S,6aS) and (3aS,4S,6S,6aS)-3a-hydroxymethyl-2,2-dimethyl-6-vinyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aS,4R,6S,6aS) and (3aS,4S,6S,6aS)-3a-hydroxymethyl-2,2-dimethyl-6-vinyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-ol
• 英文别名: (-)-(3aS,4R/S,6S,6aS)-3a-hydroxymethyl-2,2-dimethyl-6-vinyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol；(3aS,6S,6aS)-3a-hydroxymethyl-2,2-dimethyl-6-vinyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol；(3aS,6S,6aS)-6-ethenyl-3a-(hydroxymethyl)-2,2-dimethyl-6,6a-dihydro-4H-furo[3,4-d][1,3]dioxol-4-ol
• 化学式: C₁₀H₁₆O₅
• 分子量: 216.234
• InChiKey: LNQKLEUZVWZPGC-ABZRCEQJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3aS,4R,6S,6aS) and (3aS,4S,6S,6aS)-3a-hydroxymethyl-2,2-dimethyl-6-vinyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-ol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 4-二甲氨基吡啶 、 potassium tert-butylate 、 三乙胺 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 为溶剂， 反应 38.5h， 生成 methanesulfonic acid (3aS,4S,6aS)-2,2-dimethyl-6a-trityloxymethyl-4,6a-dihydro-3aH-cyclopenta[1,3]dioxol-4-yl ester
  参考文献：
  名称：

  立体选择性合成新型的奈普兰球蛋白A的apio类似物作为潜在的S-腺苷同型半胱氨酸水解酶抑制剂。

  摘要：

  从D-核糖开始，通过立体选择性羟甲基化和RCM反应，完成了apio-neplanocin A的总合成，该合成结合了apio核苷和neplanocin A的特性，并且是S-腺苷同型半胱氨酸水解酶的潜在抑制剂。[反应：看文字]

  DOI：

  10.1021/ol026624m
• 作为产物：
  描述：

  (R)-1-((4R,5S)-5-((S)-1-hydroxyallyl)-2,2-dimethyl-1,3-dioxolan-4-yl)ethane-1,2-diol 在 sodium periodate 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 36.67h， 生成 (3aS,4R,6S,6aS) and (3aS,4S,6S,6aS)-3a-hydroxymethyl-2,2-dimethyl-6-vinyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-ol
  参考文献：
  名称：

  立体选择性合成新型的奈普兰球蛋白A的apio类似物作为潜在的S-腺苷同型半胱氨酸水解酶抑制剂。

  摘要：

  从D-核糖开始，通过立体选择性羟甲基化和RCM反应，完成了apio-neplanocin A的总合成，该合成结合了apio核苷和neplanocin A的特性，并且是S-腺苷同型半胱氨酸水解酶的潜在抑制剂。[反应：看文字]

  DOI：

  10.1021/ol026624m

文献信息

• Stereoselective Synthesis of a Novel Apio Analogue of Neplanocin A as Potential <i>S</i>-Adenosylhomocysteine Hydrolase Inhibitor
  作者：Hyung Ryong Moon、Hea Ok Kim、Kang Man Lee、Moon Woo Chun、Joong Hyup Kim、Lak Shin Jeong

  DOI：10.1021/ol026624m

  日期：2002.10.1

  A total synthesis of apio-neplanocin A, which combines properties of apio nucleoside and neplanocin A and is a potential inhibitor of S-adenosylhomocysteine hydrolase, was accomplished starting from D-ribose via stereoselective hydroxymethylation and RCM reaction. [reaction: see text]

  从D-核糖开始，通过立体选择性羟甲基化和RCM反应，完成了apio-neplanocin A的总合成，该合成结合了apio核苷和neplanocin A的特性，并且是S-腺苷同型半胱氨酸水解酶的潜在抑制剂。[反应：看文字]
• STEREOSELECTIVE SYNTHESIS OF CONFORMATIONALLY RIGID APIO CARBANUCLEOSIDES AS POTENTIAL ANTIVIRAL AGENTS
  作者：Hyung Ryong Moon、Kyung Ran Kim、Bum Tae Kim、Ki Jun Hwang、Moon Woo Chun、Lak Shin Jeong

  DOI：10.1081/ncn-200060292

  日期：2005.4.1

  Apio north-methanocarbocyclic nucleosides 1–3 with bicyclo[3.1.0]hexane template were first synthesized. Introduction of hydroxymethyl substituent was efficiently and stereoselectively accomplished by aldol and retro-aldol reaction and fixed conformation was achieved from a modified Simmons-Smith cyclopropanation on a cyclopentane ring.

  首次合成了以双环[3.1.0] 己烷为模板的 Apio 北-甲烷碳环核苷 1-3。羟甲基取代基的引入通过羟醛和逆羟醛反应有效且立体选择性地完成，固定构象由环戊烷环上的改性 Simmons-Smith 环丙烷化实现。
• Synthesis of Novel Apio Carbocyclic Nucleoside Analogues as Selective A₃ Adenosine Receptor Agonists
  作者：Jeong A Lee、Hyung Ryong Moon、Hea Ok Kim、Kyung Ran Kim、Kang Man Lee、Bum Tae Kim、Ki Jun Hwang、Moon Woo Chun、Kenneth A. Jacobson、Lak Shin Jeong

  DOI：10.1021/jo0503207

  日期：2005.6.1

  the properties of two nucleosides, were stereoselectively synthesized. The apio moiety of the target nucleosides 5a−d was stereoselectively introduced by treating lactol 10 with 37% formaldehyde in the presence of potassium carbonate. The carbasugar moiety of neplanocin A was successively built by exposing diene 12 on a Grubbs catalyst in methylene chloride. The final nucleosides 5a−d were synthesized

  基于内啡肽A和apio-dideoxyadenosine（apio-ddA）的生物学活性，立体选择性地合成了新的apio-neplanocin A类似物5a - d，结合了两个核苷的特性。通过在碳酸钾存在下用37％甲醛处理乳糖醇10，立体选择性地引入靶核苷5a - d的apio部分。通过将二烯12暴露在二氯甲烷中的Grubbs催化剂上来连续构建neplanocin A的羧化糖部分。最终核苷5a - d由糖基供体14的缩合合成在标准的Mitsunobu条件下使用核酸碱基。同样，apio-aristeromycin 6和（N）-apio-methanocarbaadenosine 7是使用催化氢化和Simmons-Smith环丙烷化为关键步骤从共同的中间体13衍生而来的。所有最终的核苷5a - d，6和7均未显示出对高达100μM的S-腺苷同型半胱氨酸水解酶（SAH）的显着抑制活性，这可能是由
• Asymmetric Synthesis of Novel Apio Carbocyclic Nucleoside Analogues as Potential Antiviral and Antitumor Agent
  作者：Lak Shin Jeong、Jeong A. Lee、Hyung Ryong Moon、Hea Ok Kim、Kang Man Lee、Hyun Joo Lee、Moon Woo Chun

  DOI：10.1080/15257770701493237

  日期：2007.11.26

  Novel apio carbocyclic nucleosides 18–21 were asymmetrically synthesized as potential antiviral and antitumor agent, starting from D-ribose employing aldol reaction, RCM reaction and Mitsunobu reaction as key reactions.

  从D-核糖开始，采用醛醇反应，RCM反应和Mitsunobu反应作为关键反应，从D-核糖开始不对称合成新型的无脂碳环核苷18-21作为潜在的抗病毒剂和抗肿瘤剂。
• Lead tetraacetate mediated one pot oxidative cleavage and acetylation reaction: an approach to apio and homologated apio pyrimidine nucleosides and their anticancer activity
  作者：Amarendra Panda、Sehbanul Islam、Manas Kumar Santra、Shantanu Pal

  DOI：10.1039/c5ra19080k

  日期：——

  efficient and versatile strategy of general applicability towards apio and homologated apio pyrimidines has been delineated. The methodology shows tosylation followed by in situ cyclization and one pot oxidative cleavage and acetylation by Pb(OAc)4 as the key steps. The methodology has been applied to D-ribose and D-mannose derivatives to achieve asymmetric synthesis of apio and homologated apio pyrimidine

  已经描述了对apio和同源的apio嘧啶具有普遍适用性的有效且通用的策略。该方法显示了甲苯磺酸化，原位环化，一锅氧化裂解和Pb（OAc）4的乙酰化是关键步骤。该方法已经应用于D-核糖和D-甘露糖衍生物以实现apio和同源apio嘧啶核苷的不对称合成。