S-2-Pyridyl (R)-3-tert-butyldimethylsilyloxybutanoate | 141781-29-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: S-2-Pyridyl (R)-3-tert-butyldimethylsilyloxybutanoate
• 英文别名: S-pyridin-2-yl (3R)-3-[tert-butyl(dimethyl)silyl]oxybutanethioate
• CAS: 141781-29-5
• 化学式: C₁₅H₂₅NO₂SSi
• 分子量: 311.52
• InChiKey: NVLCQVXEFCYGFN-GFCCVEGCSA-N

物化性质

• 沸点：
  368.7±22.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  64.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  S-2-Pyridyl (R)-3-tert-butyldimethylsilyloxybutanoate 、 在 四氯化钛 、 三乙胺 作用下， 以23%的产率得到3-<1-<<(1,1-dimethylethyl)dimethylsilyl>oxy>ethyl>-4-<2-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-methylethyl>-1-(phenylethyl)-2-azetidinone
  参考文献：
  名称：

  通过手性2-吡啶硫基酯的烯醇钛与手性亚胺的缩合，高度立体选择性地合成β-内酰胺

  摘要：

  衍生自（R）-3-羟基丁炔酸的2-吡啶基硫代锡的钛烯醇与手性亚胺的反应以高度选择性的方式提供了3,3'-抗-3,4-反式构型的β-内酰胺。该方法已应用于碳青霉烯抗生素1β-甲基噻吩霉素的前体的合成。

  DOI：

  10.1016/0040-4020(95)00574-r
• 作为产物：
  描述：

  ethyl (R)-3-[(tert-butyldimethylsilyl)oxy]butanoate 在 sodium hydroxide 、 三苯基膦 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 S-2-Pyridyl (R)-3-tert-butyldimethylsilyloxybutanoate
  参考文献：
  名称：

  Stereoselective synthesis of .beta.-lactams by condensation of titanium enolates of 2-pyridyl thioesters with imines

  摘要：

  A mild and versatile one-pot synthesis of beta-lactams has been performed by condensation of the easily generated titantium enolates of 2-pyridyl thioesters with imines employing chiral reaction partners. Both imines obtained from enantiomerically pure alkoxy aldehydes and the enolate derived from 3-hydroxybutyrate showed high diastereofacial preferences, efficiently transferring the stereochemical information to the stereocenters of the azetidinone ring. Advanced precursors of (+)-PS-5, (+)-PS-6, thienamycin, and 1-beta-methylthienamycin were prepared to illustrate the potential of this method. A H-1-NMR study of the enolization process and a tentative rationalization of the stereochemical results are presented.

  DOI：

  10.1021/jo00041a019

文献信息

• A Novel Approach to the Synthesis of Precursors of Tricyclic β-Lactam Antibiotics
  作者：Rita Annunziata、Maurizio Benaglia、Mauro Cinquini、Franco Cozzi、Laura Poletti、Laura Raimondi、Alcide Perboni

  DOI：10.1002/(sici)1099-0690(199911)1999:11<3067::aid-ejoc3067>3.0.co;2-k

  日期：1999.11

  The stereoselective synthesis of two precursors of tricyclic β-lactam antibiotics (trinems) has been attempted by a novel approach that involves a highly stereoselective azetidinone ring-forming reaction followed by the reduction of a functionalized aromatic substituent at C-4 of the β-lactam nucleus.

  已经尝试了一种新方法来立体选择性合成三环β-内酰胺抗生素（三嗪类）的两种前体，该方法涉及高度立体选择性氮杂环丁酮成环反应，然后还原β-内酰胺C-4上的官能化芳族取代基核。
• Synthesis of β-lactams by condensation of the tin enolates of 2-pyridylthioesters with imines. A comparison between titanium and tin enolates
  作者：Rita Annunziata、Maurizio Benaglia、Mauro Cinquini、Franco Cozzi、Laura Raimondi

  DOI：10.1016/s0040-4020(01)85649-0

  日期：1994.1

  SnBr4 affords the corresponding tin(IV) enolates that add to imines to give β-lactams in fair to good yields and with various degree of trans/cis stereoselectivity. Examples of highly diastereofacially selective reactions carried out on a chiral thioester and on a chiral imine are also reported. The results are compared with those obtained in the condensations promoted by TiCl4 and TiBr4.

  将三乙胺加到2-吡啶基硫代酯和SnCl 4或SnBr 4的混合物中，得到相应的锡（IV）烯醇盐，它们加到亚胺上，以公平至良好的收率和不同程度的反式/顺式立体选择性得到β-内酰胺。还报道了在手性硫酯和手性亚胺上进行的高度非对映选择性反应的实例。将结果与由TiCl 4和TiBr 4促进的缩合中获得的结果进行比较。
• Soluble polymer-supported synthesis of imines and β-lactams
  作者：Valentina Molteni、Rita Annunziata、Mauro Cinquini、Franco Cozzi、Maurizio Benaglia

  DOI：10.1016/s0040-4039(97)10770-5

  日期：1998.3

  The first synthesis of β-lactams bound to a soluble/insoluble polyethylene glycol monomethylether polymeric matrix has been realized by standard reactions carried out on immobilized imines. β-Lactams removal from the polymer has been accomplished under acidic and basic conditions.

  通过在固定化的亚胺上进行的标准反应，已经实现了与可溶/不可溶的聚乙二醇单甲醚聚合物基体结合的β-内酰胺的首次合成。从聚合物中去除β-内酰胺是在酸性和碱性条件下完成的。
• Synthesis of β-lactams by condensation of titanium enolates of 2-pyridylthioesters with imines. Influence of the imine structure on the trans/cis stereoselectivity
  作者：Rita Annunziata、Maurizio Benaglia、Mauro Cinquini、Franco Cozzi、Francesco Ponzini、Laura Raimondi

  DOI：10.1016/s0040-4020(01)87005-8

  日期：1994.2

  The condensation of the titanium enolates of C-2 alkyl substituted 2-pyridylthioesters with imines affords beta-lactams in trans/cis ratios that largely depend on the structure of the C-imine residue. Bulky and non-chelating heteroatom-containing groups lead to the formation of trans p-lactams, while sterically non-requiring or chelating groups favour the formation of the cia-products. On the basis of NMR evidences a rationale is proposed to account for the observed stereoselectivity.
• Soluble-Polymer-Supported Synthesis ofβ-Lactams on a Modified Poly(ethylene glycol)
  作者：Rita Annunziata、Maurizio Benaglia、Mauro Cinquini、Franco Cozzi

  DOI：10.1002/(sici)1521-3765(20000103)6:1<133::aid-chem133>3.0.co;2-h

  日期：2000.1.3

  A modified poly(ethylene glycol) (PEG) has been developed for the soluble-polymer-supported synthesis of beta-lactams. The monomethylether of PEG (MeOPEG) with an average M-W of 5000 was used as the support, a 4-(3-propyl)phenyl residue as the spacer, and a 4-oxyphenylamino group as the moiety with the reactive functionality. From this modified PEG representative aromatic, heteroaromatic, unsaturated, and aliphatic imines were obtained in high yields by different procedures. The polymer-supported imines were then employed to prepare several beta-lactams by enolate/imine condensation and ketene/imine cycloaddition. Examples of the control of the absolute stereochemistry during the azetidinone ring formation are also reported. The reactions carried out on the polymer-bound imines showed a remarkable similarity to those performed on nonimmobilized imines, both in terms of yields and stereoselectivities. Removal of the beta-lactams from the polymer has also been accomplished to directly deliver the N-unsubstituted azetidinones.