L-(+)-2-<(methylthio)methyl>pyrrolidine | 106865-55-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: L-(+)-2-<(methylthio)methyl>pyrrolidine
• 英文别名: (S)-2-<(methylthio)methyl>pyrrolidine；(S)-2-[(methylthio)methyl]pyrrolidine；(2S)-2-[(methylsulfanyl)methyl]pyrrolidine；(2S)-2-(methylsulfanylmethyl)pyrrolidine
• CAS: 106865-55-8
• 化学式: C₆H₁₃NS
• 分子量: 131.242
• InChiKey: UAFBQROGXTXREC-LURJTMIESA-N

物化性质

• 沸点：
  60-63 °C(Press: 30 Torr)
• 密度：
  0.962±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  L-(+)-2-<(methylthio)methyl>pyrrolidine 在 lithium bromide 作用下， 以 乙腈 为溶剂， 反应 49.17h， 生成
  参考文献：
  名称：

  Asymmetric synthesis of 3-substituted 2-exo-methylenealkanones by addition-elimination reaction using a chiral leaving group and organometallic nucleophiles

  摘要：

  A novel diastereodifferentiating addition-elimination reaction of (S)-2-[[2-(methoxymethyl)-1-pyrrolidinyl]methyl]-2-alken-1-ones with organometallic reagents such as organocuprates and organozincates afforded optically active 3-substituted 2-methylenealkanones with high enantiomeric purity. The enantiomeric excess (ee) of the products in this asymmetric induction reaction involving 1,5-transfer of stereogenicity was highly dependent on the structure of the enone substrates and the type of organometallic reagents, chiral auxiliaries, and added Lewis acids: (i) the use of lithium diorganocuprates (R2CuLi) led to the highest ee's, (ii) in the reaction with R2CuLi the ee decreased in the following order by varying their structure of the main framework of the enones, cycloheptenones (96-97% ee) > cyclohexenones (95% ee) > cyclopentenones (82-85% ee) > acyclic enones (55-70% ee), (iii) the addition of LiBr as the external Lewis acid in the reaction with R2CuLi did not affect the ee, whereas that of ZnBr2 or MgBr2 decreased the ee by 5% or considerably more, respectively, and (iv) the existence of the methoxy oxygen atom in the chiral auxiliary was essential to achieve high ee's. The origin of the observed high and low ee's was rationalized by considering plausible transition state models.

  DOI：

  10.1021/jo00044a026
• 作为产物：
  描述：

  tert-butyl (2S)-2-{[(methylsulfonyl)oxy]methyl}-pyrrolidine-1-carboxylate 在 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 240.5h， 生成 L-(+)-2-<(methylthio)methyl>pyrrolidine
  参考文献：
  名称：

  Asymmetric synthesis of 3-substituted 2-exo-methylenealkanones by addition-elimination reaction using a chiral leaving group and organometallic nucleophiles

  摘要：

  A novel diastereodifferentiating addition-elimination reaction of (S)-2-[[2-(methoxymethyl)-1-pyrrolidinyl]methyl]-2-alken-1-ones with organometallic reagents such as organocuprates and organozincates afforded optically active 3-substituted 2-methylenealkanones with high enantiomeric purity. The enantiomeric excess (ee) of the products in this asymmetric induction reaction involving 1,5-transfer of stereogenicity was highly dependent on the structure of the enone substrates and the type of organometallic reagents, chiral auxiliaries, and added Lewis acids: (i) the use of lithium diorganocuprates (R2CuLi) led to the highest ee's, (ii) in the reaction with R2CuLi the ee decreased in the following order by varying their structure of the main framework of the enones, cycloheptenones (96-97% ee) > cyclohexenones (95% ee) > cyclopentenones (82-85% ee) > acyclic enones (55-70% ee), (iii) the addition of LiBr as the external Lewis acid in the reaction with R2CuLi did not affect the ee, whereas that of ZnBr2 or MgBr2 decreased the ee by 5% or considerably more, respectively, and (iv) the existence of the methoxy oxygen atom in the chiral auxiliary was essential to achieve high ee's. The origin of the observed high and low ee's was rationalized by considering plausible transition state models.

  DOI：

  10.1021/jo00044a026

文献信息

• A Highly Stereoselective Synthesis of Glycidic Amides Based on a New Class of Chiral Sulfonium Salts: Applications in Asymmetric Synthesis
  作者：Francisco Sarabia、Carlos Vivar-García、Miguel García-Castro、Cristina García-Ruiz、Francisca Martín-Gálvez、Antonio Sánchez-Ruiz、Samy Chammaa

  DOI：10.1002/chem.201201332

  日期：2012.11.19

  A new type of chiral sulfonium salts that are characterized by a bicyclic system has been designed and synthesized from α‐amino acids. Their corresponding ylides, which were prepared by basic treatment of the sulfonium salts, reacted smoothly with a broad array of simple and chiral aldehydes to provide trans‐epoxy amides in reasonable to very good yields and excellent stereoselectivities (>98 %). The

  由α-氨基酸设计并合成了一种新型的具有双环体系特征的手性sulf盐。通过对treatment盐进行碱性处理而制备的它们相应的酰基化物，可与各种简单的手性醛平稳地反应，以合理至非常高的收率和出色的立体选择性（> 98％）提供反式环氧酰胺。发现获得的环氧酰胺可用作合成构件。因此，它们被还原成相应的环氧醇，并与不同类型的亲核试剂进行环氧乙烷开环反应。
• Asymmetric induction in the conjugate addition reactions of chiral organo(hetero)cuprates
  作者：R. Karl Dieter、Maritherese Tokles

  DOI：10.1021/ja00241a021

  日期：1987.4
• Synthesis of chiral β-amino sulfides and β-amino thiols from α-amino acids
  作者：Graeme A. Cran、Colin L. Gibson、Sheetal Handa

  DOI：10.1016/0957-4166(95)00197-w

  日期：1995.7

  Bifurcated routes to two series of chiral secondary beta-amino sulfides 5a - c and 11a - c have been developed from L-proIine and (S)-phenylglycine, respectively. The developed methodology has also led to the synthesis of the tertiary beta-amino thiol 7 and the primary beta-amino sulfide 1 2 from L-proline and (S)-phenylglycine, respectively.
• DIETER R. K.; TOKLES M., J. AMER. CHEM. SOC., 109,(1987) N 7, 2040-2046
  作者：DIETER R. K.、 TOKLES M.

  DOI：——

  日期：——
• MELANOCORTIN SUBTYPE-2 RECEPTOR (MC2R) ANTAGONISTS AND USES THEREOF
  申请人：Crinetics Pharmaceuticals, Inc.

  公开号：US20210002254A1

  公开（公告）日：2021-01-07

  Described herein are compounds that are melanocortin subtype-2 receptor (MC2R) modulators, methods of making such compounds, pharmaceutical compositions and medicaments comprising such compounds, and methods of using such compounds in the treatment of conditions, diseases, or disorders that would benefit from modulation of MC2R activity.