BOC-D-焦谷氨酸甲酯 | 128811-48-3

• 物质功能分类: 生物化工 - 氨基酸及其衍生物 - 谷氨酸类衍生物
• 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
• 中文名称: BOC-D-焦谷氨酸甲酯
• 中文别名: Boc-D-焦谷氨酸甲酯；N-叔丁氧羰基-D-焦谷氨酸甲酯；R-N-BOC-焦谷氨酸甲酯；N-叔丁氧羰基-L-焦谷氨酸甲酯；1-Boc-5-氧代-D-脯氨酸甲酯
• 英文名称: 1-(tert-butyl) 2-methyl (R)-5-oxopyrrolidine-1,2-dicarboxylate
• 英文别名: N-Boc-D-pyroglutamic acid methyl ester；1-(tert-butyl) 2-methyl (2R)-5-oxopyrrolidine-1,2-dicarboxylate；(R)-1-tert-butyl 2-methyl 5-oxopyrrolidine-1,2-dicarboxylate；1-O-tert-butyl 2-O-methyl (2R)-5-oxopyrrolidine-1,2-dicarboxylate
• CAS: 128811-48-3
• 化学式: C₁₁H₁₇NO₅
• 分子量: 243.26
• InChiKey: FNTAOUUEQHKLIU-SSDOTTSWSA-N

物化性质

• 熔点：
  68-69℃
• 沸点：
  361.6±35.0 °C(Predicted)
• 密度：
  1.209

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 海关编码：
  2933790090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: Methyl (R)-N-(tert-butoxycarbonyl)pyroglutamate
Synonyms:

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.

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Section 3. Composition/information on ingredients.
Ingredient name: Methyl (R)-N-(tert-butoxycarbonyl)pyroglutamate
CAS number: 128811-48-3

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Section 4. First aid measures
Skin contact: Immediately wash skin with copious amounts of water for at least 15 minutes while removing
contaminated clothing and shoes. If irritation persists, seek medical attention.
Eye contact: Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
flushing of the eyes by separating the eyelids with fingers. If irritation persists, seek medical
attention.
Inhalation: Remove to fresh air. In severe cases or if symptoms persist, seek medical attention.
Ingestion: Wash out mouth with copious amounts of water for at least 15 minutes. Seek medical attention.

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Section 5. Fire fighting measures
In the event of a fire involving this material, alone or in combination with other materials, use dry
powder or carbon dioxide extinguishers. Protective clothing and self-contained breathing apparatus
should be worn.

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Section 6. Accidental release measures
Personal precautions: Wear suitable personal protective equipment which performs satisfactorily and meets local/state/national
standards.
Respiratory precaution: Wear approved mask/respirator
Hand precaution: Wear suitable gloves/gauntlets
Skin protection: Wear suitable protective clothing
Eye protection: Wear suitable eye protection
Methods for cleaning up: Mix with sand or similar inert absorbent material, sweep up and keep in a tightly closed container
for disposal. See section 12.
Environmental precautions: Do not allow material to enter drains or water courses.

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Section 7. Handling and storage
Handling: This product should be handled only by, or under the close supervision of, those properly qualified
in the handling and use of potentially hazardous chemicals, who should take into account the fire,
health and chemical hazard data given on this sheet.
Store in closed vessels, refrigerated.
Storage:

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Section 8. Exposure Controls / Personal protection
Engineering Controls: Use only in a chemical fume hood.
Personal protective equipment: Wear laboratory clothing, chemical-resistant gloves and safety goggles.
General hydiene measures: Wash thoroughly after handling. Wash contaminated clothing before reuse.

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Section 9. Physical and chemical properties
Appearance: Not specified
Boiling point: No data
No data
Melting point:
Flash point: No data
Density: No data
Molecular formula: C11H17NO5
Molecular weight: 243.3

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Section 10. Stability and reactivity
Conditions to avoid: Heat, flames and sparks.
Materials to avoid: Oxidizing agents.
Possible hazardous combustion products: Carbon monoxide, nitrogen oxides.

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Section 11. Toxicological information
No data.

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Section 12. Ecological information
No data.

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Section 13. Disposal consideration
Arrange disposal as special waste, by licensed disposal company, in consultation with local waste
disposal authority, in accordance with national and regional regulations.

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Section 14. Transportation information
Non-harzardous for air and ground transportation.

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Section 15. Regulatory information
No chemicals in this material are subject to the reporting requirements of SARA Title III, Section
302, or have known CAS numbers that exceed the threshold reporting levels established by SARA
Title III, Section 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  BOC-D-焦谷氨酸甲酯 在 草酰氯 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 反应 1.0h， 生成 1-O-tert-butyl 2-O-methyl (2S)-4-benzoyl-5-oxopyrrolidine-1,2-dicarboxylate
  参考文献：
  名称：

  （S）-2-氨基-3-（2,5-二氢-5-氧代-4-异恶唑基）丙酸（TAN-950 A）衍生物的合成和生物活性。

  摘要：

  （S）-2-氨基-3-（2,5-二氢-5-氧代-4-异恶唑基）丙酸（TAN-950 A（1））是一种新型氨基酸抗生素，对谷氨酸受体具有高亲和力中枢神经系统。为了提高对谷氨酸受体的亲和力，研究了TAN-950 A衍生物6a-o，15a-o的构效关系。以（S）-和（R）-N-Boc-焦谷氨酸甲酯（8）为起始原料，通过C-4位的酰化反应合成旋光性TAN-950 A类似物15a-h，然后与羟胺形成异恶唑酮并随后脱保护反应。将由（RS）-氨基己二酸和（R）-和（S）-天冬氨酸的二甲酯19制备的内酰胺16转化为（RS）-3-甲基-homo-TAN-950 A（15i）和利用相似的反应序列分别对光学活性的nor-TAN-950 A衍生物15j-o进行了研究。大多数TAN-950 A衍生物6a-o，15a-o对谷氨酸受体具有亲和力。3-烷基衍生物15b，d-g特别显示出对喹喹啉亚型受体的高亲和力，并对海马

  DOI：

  10.1248/cpb.39.1199
• 作为产物：
  描述：

  D-焦谷氨酸 在 盐酸 、 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 48.0h， 生成 BOC-D-焦谷氨酸甲酯
  参考文献：
  名称：

  甲磺酸介导的环化和 γ-氨基炔酮的 Meyer-Schuster 重排：获得对映纯吡咯烷环外乙烯基酰胺

  摘要：

  α-和β-氨基炔酮已被广泛用于在各种亲电子试剂如质子酸或金（I）存在下制备杂环。在本文中，我们公开了前所未有的吡咯烷外环乙烯基酰胺的形成，以代替预期的氮杂酮或哌啶酮，从氨基酸衍生的 γ-氨基炔酮开始。该过程包括将受保护的氮串联 1,2-加成到羰基，然后进行 Meyer-Schuster 重排，从而有效地提供对映体纯的吡咯烷外环乙烯基酰胺。该序列被金盐催化的效果很差，但在甲磺酸的存在下被证明是非常有效的。

  DOI：

  10.1002/ejoc.201402336

文献信息

• Stereocontrolled Total Synthesis of (−)-Kaitocephalin
  作者：Rishi G. Vaswani、A. Richard Chamberlin

  DOI：10.1021/jo702329z

  日期：2008.3.1

  scalable synthetic route profits from the strategic utilization of substrate-controlled manipulations for the iterative installation of the requisite stereogenic centers. The key transformations include a diastereoselective modified Claisen condensation, a chemo- and diastereoselective reduction of a β-keto ester, and the substrate-directed hydrogenation of a dehydroamino ester derivative. During the course

  本文描述了基于吡咯烷的生物碱 (-)-kaitocephalin 的全化学合成的立体控制策略的成功实施。这种可扩展的合成路线得益于对底物控制操作的战略利用，以迭代安装必要的立体中心。关键转化包括非对映选择性修饰的克莱森缩合、β-酮酯的化学和非对映选择性还原以及脱氢氨基酯衍生物的底物导向氢化。在我们的研究过程中，发现了一个有趣的立体收敛环化反应，用于高效组装 kaitocephalin 2,2,5-三取代的吡咯烷核心。
• Methanesulfonic Acid Mediated Cyclization and Meyer-Schuster Rearrangement of γ-Amino-ynones: Access to Enantiopure Pyrrolidine Exocyclic Vinylogous Amides
  作者：Huy-Dinh Vu、Jacques Renault、Thierry Roisnel、Nicolas Gouault、Philippe Uriac

  DOI：10.1002/ejoc.201402336

  日期：2014.7

  protic acids or gold(I). Herein we disclose the unprecedented formation of pyrrolidine exocyclic vinylogous amides, in place of the expected azepinones or piperidinones, starting from γ-amino-ynones derived from amino acids. The process involves a tandem 1,2-addition of the protected nitrogen to the carbonyl group followed by a Meyer–Schuster rearrangement, which efficiently afforded enantiopure pyrrolidine

  α-和β-氨基炔酮已被广泛用于在各种亲电子试剂如质子酸或金（I）存在下制备杂环。在本文中，我们公开了前所未有的吡咯烷外环乙烯基酰胺的形成，以代替预期的氮杂酮或哌啶酮，从氨基酸衍生的 γ-氨基炔酮开始。该过程包括将受保护的氮串联 1,2-加成到羰基，然后进行 Meyer-Schuster 重排，从而有效地提供对映体纯的吡咯烷外环乙烯基酰胺。该序列被金盐催化的效果很差，但在甲磺酸的存在下被证明是非常有效的。
• Enantioselective synthesis of (+)-anatoxin-a via enyne metathesis
  作者：Jehrod B. Brenneman、Rainer Machauer、Stephen F. Martin

  DOI：10.1016/j.tet.2004.06.021

  日期：2004.8

  A concise synthesis of the potent nAChR agonist (+)-anatoxin-a (1) has been completed by a series of nine chemical operations and in 27% overall yield from commercially available d-methyl pyroglutamate (12). The strategy featured the application of a new protocol for the diastereoselective synthesis of cis-2,5-disubstituted pyrrolidines bearing unsaturated side chains and an intramolecular enyne metathesis

  有效的n AChR激动剂（+）-毒素-a（1）的简明合成已通过一系列九次化学操作完成，并且可从市售的d-甲基焦谷氨酸（12）中获得27％的总收率。该策略的非对映合成功能的新的协议的应用顺式-2,5-二取代的吡咯烷轴承不饱和侧链和分子内烯炔复分解以提供桥接的双环框架1。因此，焦磷酸谷氨酸甲酯（12）在五个步骤中转化为32，然后进行了简单的烯炔复分解以生成双环二烯33。在33中较少取代的碳-碳双键的选择性氧化裂解，然后脱保护得到的（+）-毒素A（1）。
• Approaches to the Synthesis of Cytochalasans Part9. A versatile concept leading to all structural types of cytochalasans
  作者：Jean Ackermann、Michael Matthes、Christoph Tamm

  DOI：10.1002/hlca.19900730113

  日期：1990.1.31

  Starting from D-glutamic acid (5), the bicyclic compounds 4a and 4b were synthesized via17 (Schemes 1 and 2). The reaction leading to 4g and 4h with LiCuPh2 was not successful. But treatment of the N-protected model lactams 19, 21, and 22 with Li2Cu(CN)Ph2 gave the amino ketones 24, 26, and 27, respectively (Scheme 3). The desired compound 23 was obtained from 20. Conversion of the unprotected lactams

  从D-谷氨酸（5）开始，通过17（方案1和2）合成了双环化合物4a和4b。用LiCuPh 2导致4g和4h的反应不成功。但治疗N-保护的模型的内酰胺19，21，和22与Li 2的Cu（CN）PH 2，得到氨基酮24，26，和27，分别为（方案3）。所需化合物23从得到20转换未受保护内酰胺的28，31，和32，得到苯基衍生物34以优良产率。酯35被转化为α-氨基-γ-氧代酸衍生物36。这种转化打开了对这类化合物的新颖途径。
• Design and Synthesis of Diversely Substituted Azacyclic Inhibitors of Endothelin Converting Enzyme
  作者：Stephen Hanessian、Cécile Gauchet、Guillaume Charron、Julien Marin、Philippe Nakache

  DOI：10.1021/jo052649y

  日期：2006.3.31

  azacyclic phosphonic acids were synthesized from l-pyroglutamic acid, 6-oxo-l-pipecolic acid, and their enantiomers. The objective was to study the effect of constraining acyclic inhibitors of endothelin converting enzyme on inhibitory activity. Potential pharmacophoric tethers were introduced by stereocontrolled reactions to give highly substituted pyrrolidine- and piperidine-α-phosphonic acids. Weak

  由1-焦谷氨酸，6-氧-1-哌酸及其对映异构体合成了一系列氮杂环膦酸。目的是研究限制内皮素转化酶的无环抑制剂对抑制活性的影响。通过立体控制反应引入潜在的药效学系链，以得到高度取代的吡咯烷-和哌啶-α-膦酸。对于每个具有相同取代基相对取向的系列的非对映异构体，观察到了弱的抑制活性。