Allylated Boc-cysteine ethyl ester

• 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: Allylated Boc-cysteine ethyl ester
• 英文别名: ethyl (2R)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-prop-2-enylsulfanylpropanoate
• 化学式: C₁₃H₂₃NO₄S
• 分子量: 289.396
• InChiKey: ZNVBFVXUNUCZED-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  19
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  89.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-diazo-2-(dimethoxyphosphoryl)acetate 、 Allylated Boc-cysteine ethyl ester 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 以41%的产率得到2-((R)-2-tert-Butoxycarbonylamino-2-ethoxycarbonyl-ethylsulfanyl)-2-(dimethoxy-phosphoryl)-pent-4-enoic acid methyl ester
  参考文献：
  名称：

  New Strategies to Cyclic α-Thiophosphonates

  摘要：

  报告了一种过渡金属催化的环状δ±-硫代磷酸酯的方法。该策略包括 Rh2(OAc)4 催化的δ-二氮膦酸盐生成的中间硫酰基的[2,3]-三向异性重排，以及由此生成的δ-硫代磷酸盐 2 a - c 的闭环偏析 (RCM)，从而生成官能化的环状δ-硫代磷酸盐 4 a - c。

  DOI：

  10.1055/s-2001-13374
• 作为产物：
  描述：

  N-Boc-L-cysteine ethyl ester 、 3-溴丙烯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 以78%的产率得到Allylated Boc-cysteine ethyl ester
  参考文献：
  名称：

  Synthesis of S-glycosyl amino acids and S-glycopeptides via photoinduced click thiol–ene coupling

  摘要：

  We report on the photoinduced addition of glycosyl thiols to alkenyl glycines (thiol-ene coupling) to give S-glycosyl amino acids in high yields (53-90%). One of the amino acids thus prepared was used in the construction of a tripeptide via solution phase chemistry. Moreover, a one-pot two-step approach to an S-glycopeptide was developed using glutathione (GSH) as model starting material. This approach involved GSH S-alkenylation followed by photoinduced hydrothiolation by a glycosyl thiol. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.11.097

文献信息

• Sigmatropic Rearrangements as Tools for Amino Acid and Peptide Modification:  Application of the Allylic Sulfur Ylide Rearrangement to the Preparation of Neoglycoconjugates and Other Conjugates
  作者：David Crich、Yekui Zou、Franck Brebion

  DOI：10.1021/jo061439y

  日期：2006.11.1

  Reaction of S-allyl cysteine derivatives, generated by the selenocysteine ligation, with rhodium carbenoids, stabilized and unstabilized, enables the attachment of diverse functionality onto cysteine residues. The reaction is successfully applied to the introduction of lipid-like residues, a fluorous alkyl chain, and mono- and disaccharides.

  由硒代半胱氨酸连接产生的S-烯丙基半胱氨酸衍生物与稳定和不稳定的铑类胡萝卜素的反应，可使各种功能附着于半胱氨酸残基上。该反应成功地用于引入脂质样残基，氟代烷基链以及单糖和二糖。
• Diastereoselective Alkylations of a Protected Cysteinesulfenate
  作者：Adrian L. Schwan、Marcus J. Verdu、Suneel P. Singh、Jennifer S. O’Donnell、Amir Nasser Ahmadi

  DOI：10.1021/jo901021r

  日期：2009.9.4

  To further understand stereoselection in the alkylation of sulfenate anions, a protected cysteinesulfenate was generated in THF solution at low temperature. Introduction of a reactive alkylating agent brings about a cysteinyl sulfoxide in 51-75% yield, with diastereomeric ratios at the sulfinyl group ranging from 83:17 to 95:5. An internally complexed lithium counterion is proposed to account for the stereoselectivity.
• Synthesis of S-glycosyl amino acids and S-glycopeptides via photoinduced click thiol–ene coupling
  作者：Michele Fiore、Mauro Lo Conte、Salvatore Pacifico、Alberto Marra、Alessandro Dondoni

  DOI：10.1016/j.tetlet.2010.11.097

  日期：2011.1

  We report on the photoinduced addition of glycosyl thiols to alkenyl glycines (thiol-ene coupling) to give S-glycosyl amino acids in high yields (53-90%). One of the amino acids thus prepared was used in the construction of a tripeptide via solution phase chemistry. Moreover, a one-pot two-step approach to an S-glycopeptide was developed using glutathione (GSH) as model starting material. This approach involved GSH S-alkenylation followed by photoinduced hydrothiolation by a glycosyl thiol. (C) 2010 Elsevier Ltd. All rights reserved.
• New Strategies to Cyclic <i>α</i>-Thiophosphonates
  作者：Joel D. Moore、Kevin T. Sprott、Paul R. Hanson

  DOI：10.1055/s-2001-13374

  日期：——

  A transition-metal-catalyzed approach to cyclic α-thiophosphonates is reported. This strategy incorporates both a Rh2(OAc)4-catalyzed [2,3]-sigmatropic rearrangement of intermediate sulfur-ylides generated from α-diazophosphonates and a ring-closing metathesis (RCM) of the resulting α-thiophosphonates 2 a - c to yield functionalized cyclic α-thiophosphonates 4 a - c.

  报告了一种过渡金属催化的环状δ±-硫代磷酸酯的方法。该策略包括 Rh2(OAc)4 催化的δ-二氮膦酸盐生成的中间硫酰基的[2,3]-三向异性重排，以及由此生成的δ-硫代磷酸盐 2 a - c 的闭环偏析 (RCM)，从而生成官能化的环状δ-硫代磷酸盐 4 a - c。