tert-butyl (2S)-2-[(methylthio)methyl]pyrrolidine-1-carboxylate | 143008-59-7

• 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: tert-butyl (2S)-2-[(methylthio)methyl]pyrrolidine-1-carboxylate
• 英文别名: (S)-N-Boc-2-<(methylthio)methyl>pyrrolidine；(S)-N-Boc-2-[(methylthio)methyl]pyrrolidine；(S)-tert-butyl 2-((methylthio)methyl)pyrrolidine-1-carboxylate；tert-butyl (2S)-2-(methylsulfanylmethyl)pyrrolidine-1-carboxylate
• CAS: 143008-59-7
• 化学式: C₁₁H₂₁NO₂S
• 分子量: 231.359
• InChiKey: UXFUPNXBSGBAGM-VIFPVBQESA-N

物化性质

• 沸点：
  308.6±15.0 °C(Predicted)
• 密度：
  1.058±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  54.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl (2S)-2-[(methylthio)methyl]pyrrolidine-1-carboxylate 在 三氟乙酸 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 1.5h， 生成 (E)-2-[[(2S)-2-(methylsulfanylmethyl)pyrrolidin-1-yl]methyl]-1,3-diphenylprop-2-en-1-one
  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：

  Boc-L-脯氨酸甲酯 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 tert-butyl (2S)-2-[(methylthio)methyl]pyrrolidine-1-carboxylate
  参考文献：
  名称：

  Synthesis of chiral β-amino sulfides and β-amino thiols from α-amino acids

  摘要：

  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.

  DOI：

  10.1016/0957-4166(95)00197-w

文献信息

• Selenium promoted synthesis of enantiopure pyrrolidines starting from chiral aminoalcohols
  作者：Marcello Tiecco、Lorenzo Testaferri、Luana Bagnoli、Catalina Scarponi、Andrea Temperini、Francesca Marini、Claudio Santi

  DOI：10.1016/j.tetasy.2007.11.003

  日期：2007.11

  Starting from commercially available enantiomerically pure aminoalcohols and using simple conversions promoted by organoselenium reagents, several enantiomerically pure substituted pyrrolidines were prepared. After double protections (R)- or (S)-2-phenylglycinols were converted into the beta-amino selenides by displacing the tosyl group with phenyl selenolate anions. The phenylseleno group was then substituted by an allyl group by treatment with allyltributyltin and AIBN. The reaction of these allylic derivatives with electrophilic phenylselenium reagents afforded selenium containing pyrrolidines as the result of a 5-exo-trig cyclization. The pyrrolidine derivatives thus obtained were reductively deselenylated with triphenyltin hydride and AIBN. Moreover, the selenides were converted into the selenones, which easily gave substitution with different nucleophiles. Enantiopure 2,5-pyrrolidines containing azido, methylthio, cyano and iodo groups were thus obtained. (c) 2007 Elsevier Ltd. All rights reserved.
• Asymmetric synthesis of 3-substituted 2-exo-methylenealkanones by addition-elimination reaction using a chiral leaving group and organometallic nucleophiles
  作者：Rui Tamura、Kenichiro Watabe、Noboru Ono、Yukio Yamamoto

  DOI：10.1021/jo00044a026

  日期：1992.8

  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.
• 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.