(3S,7R,7aS)-tetrahydro-7-methoxy-7,7a-dimethyl-5-oxo-2H-oxazolo[3,2-c]oxazole-3-carboxylic acid methyl ester | 945544-14-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (3S,7R,7aS)-tetrahydro-7-methoxy-7,7a-dimethyl-5-oxo-2H-oxazolo[3,2-c]oxazole-3-carboxylic acid methyl ester
• 英文别名: methyl (3S,7R,7aS)-7-methoxy-7,7a-dimethyl-5-oxotetrahydro-5H-oxazolo[4,3-b]oxazole-3-carboxylate；methyl (3S,7R,7aS)-7-methoxy-7,7a-dimethyl-5-oxo-2,3-dihydro-[1,3]oxazolo[3,2-c][1,3]oxazole-3-carboxylate
• CAS: 945544-14-9
• 化学式: C₁₀H₁₅NO₆
• 分子量: 245.232
• InChiKey: SFIOEEIERRTFCP-JMOVZRAMSA-N

物化性质

• 沸点：
  380.6±42.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  74.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3S,7R,7aS)-tetrahydro-7-methoxy-7,7a-dimethyl-5-oxo-2H-oxazolo[3,2-c]oxazole-3-carboxylic acid methyl ester 在 lithium hexamethyldisilazane 、 氯化铵-d4 、 重水 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 (4S,5R)-2-(4-hydroxy-5-methoxy-4,5-dimethyloxazolidin-2-one-3-yl)acrylic acid methyl ester
  参考文献：
  名称：

  丝氨酸、半胱氨酸、硒代半胱氨酸和 2,3-二氨基丙酸衍生物的立体选择性 α-氘化

  摘要：

  已经开发了用于合成丝氨酸、半胱氨酸、硒代半胱氨酸和 2,3-二氨基丙酸的对映体纯 α-氘代衍生物的有效方法。H/D 交换是通过手性双环丝氨酸等价物的去质子化然后选择性氘化来实现的。此外，将硫醇、硒醇和胺非对映选择性添加到氘代醇中的手性双环脱氢丙氨酸中，可以在半胱氨酸、硒代半胱氨酸和 2,3-二氨基丙酸衍生物的 Cα 原子上进行位点选择性氘化。合成了一种用于治疗支气管扩张的药物碳半胱氨酸的氘代类似物。

  DOI：

  10.1021/acs.orglett.2c02715
• 作为产物：
  描述：

  Boc-L-丝氨酸甲酯 、 2,2,3,3-四甲氧基丁烷 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以75%的产率得到(3S,7R,7aS)-tetrahydro-7-methoxy-7,7a-dimethyl-5-oxo-2H-oxazolo[3,2-c]oxazole-3-carboxylic acid methyl ester
  参考文献：
  名称：

  高度非对映选择性烷基化中金字塔状双环丝氨酸烯醇化的理论证据。

  摘要：

  由（S）-和（R）-N-Boc-丝氨酸甲酯（Boc：叔丁氧羰基）合成了新的手性丝氨酸当量及其对映异构体。在通过非对映选择性烯醇酸钾烷基化反应和随后的酸水解合成α-烷基α-氨基酸中，已证明将这些化合物用作手性结构单元。进行了理论研究，以阐明五元环状N，O-乙缩醛的形成和随后的烷基化过程（完全保留构型而发生）的立体化学结果。该特征可以用烯醇盐中间体的高度锥体化来解释。

  DOI：

  10.1002/chem.200601746

文献信息

• Role of the Countercation in Diastereoselective Alkylations of Pyramidalized Bicyclic Serine Enolates. An Easy Approach to α-Benzylserine
  作者：Gonzalo Jiménez-Osés、Carlos Aydillo、Jesús H. Busto、María M. Zurbano、Jesús M. Peregrina、Alberto Avenoza

  DOI：10.1021/jo070656b

  日期：2007.7.1

  demonstrated in the synthesis of α-benzylserine through a diastereoselective lithium enolate alkylation reaction and subsequent acid hydrolysis. The role of a coordinating countercation (lithium) in the alkylation reaction has been investigated. Theoretical studies have been performed in order to elucidate the stereochemical outcome of the alkylation process, which occurs with total retention of configuration

  在通过非对映选择性烯醇锂烷基化反应和随后的酸水解合成α-苄基丝氨酸中，已证明使用手性丝氨酸等同物作为优异的手性结构单元。已经研究了配位抗衡阳离子（锂）在烷基化反应中的作用。为了阐明烷基化过程的立体化学结果，已经进行了理论研究，该结果在完全保留构型的情况下发生。
• <i>S</i>-Michael Additions to Chiral Dehydroalanines as an Entry to Glycosylated Cysteines and a Sulfa-Tn Antigen Mimic
  作者：Carlos Aydillo、Ismael Compañón、Alberto Avenoza、Jesús H. Busto、Francisco Corzana、Jesús M. Peregrina、María M. Zurbano

  DOI：10.1021/ja411522f

  日期：2014.1.15

  Stereoselective sulfa-Michael addition of appropriately protected thiocarbohydrates to chiral dehydroalanines has been developed as a key step in the synthesis of biologically important cysteine derivatives, such as S-(beta-D-glucopyranosyl)-D-cysteine, which has not been synthesized to date, and S-(2-acetamido-2-deoxy-alpha-D-galactopyranosyl)-L-cysteine, which could be considered as a mimic of Tn antigen. The corresponding diamide derivative was also synthesized and analyzed from a conformational viewpoint, and its bound state with a lectin was studied.
• A Domino Michael/Dieckmann Process as an Entry to α-(Hydroxymethyl)glutamic Acid
  作者：Carlos Aydillo、Gonzalo Jiménez-Osés、Alberto Avenoza、Jesús H. Busto、Jesús M. Peregrina、María M. Zurbano

  DOI：10.1021/jo201067n

  日期：2011.9.2

  A domino process that involves a Michael-type addition followed by a Dieckmann reaction mediated by the participation of the cyclic carbamate group is the key step in the synthesis of both enantiomers of alpha-(hydroxymethyl)glutamic acid (HMG).
• A Double Diastereoselective Michael-Type Addition as an Entry to Conformationally Restricted Tn Antigen Mimics
  作者：Carlos Aydillo、Claudio D. Navo、Jesús H. Busto、Francisco Corzana、María M. Zurbano、Alberto Avenoza、Jesús M. Peregrina

  DOI：10.1021/jo4019396

  日期：2013.11.1

  A totally stereocontrolled C-Michael addition of serine-equivalent C-nucleophiles to tri-O-benzyl-2-nitro-D-galactal was used as the key step to synthesize several pyrano[3,2-b]pyrrole structures. These scaffolds could be regarded as conformationally restricted Tn antigen mimics, as we have demonstrated by biological assays. The pyranose rings retain their C-4(1) chair conformation, as shown by molecular modeling and NMR spectroscopy. The expected bioactivity was established by a competition-tailored enzyme-linked lectin assay using both soybean and Vicia villosa agglutinins as model lectins. The facile described synthetic route and the strategic combination of computational and experimental techniques to reveal conformational features and bioactivity demonstrate the prepared glycomimics to be promising candidates for further exploitation of this scaffold to give glycans for lectin blocking and vaccination.
• Theoretical Evidence for Pyramidalized Bicyclic Serine Enolates in Highly Diastereoselective Alkylations
  作者：Carlos Aydillo、Gonzalo Jiménez-Osés、Jesús H. Busto、Jesús M. Peregrina、María M. Zurbano、Alberto Avenoza

  DOI：10.1002/chem.200601746

  日期：2007.6.4

  and its enantiomer have been synthesized from (S)- and (R)-N-Boc-serine methyl esters (Boc: tert-butyloxycarbonyl). The use of these compounds as chiral building blocks has been demonstrated in the synthesis of alpha-alkyl alpha-amino acids by diastereoselective potassium enolate alkylation reactions and subsequent acid hydrolyses. Theoretical studies were performed to elucidate the stereochemical

  由（S）-和（R）-N-Boc-丝氨酸甲酯（Boc：叔丁氧羰基）合成了新的手性丝氨酸当量及其对映异构体。在通过非对映选择性烯醇酸钾烷基化反应和随后的酸水解合成α-烷基α-氨基酸中，已证明将这些化合物用作手性结构单元。进行了理论研究，以阐明五元环状N，O-乙缩醛的形成和随后的烷基化过程（完全保留构型而发生）的立体化学结果。该特征可以用烯醇盐中间体的高度锥体化来解释。