戴维斯试剂 | 131863-82-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 戴维斯试剂
• 英文名称: (+)-<(8,8-Dimethoxycamphoryl)sulfonyl>oxaziridine
• 英文别名: (+)-<(3,3-dimethoxycamphoryl)sulfonyl>oxaziridine；<(3,3-dimethoxycarmphoryl)sulfonyl>oxaziridine；(+)-(2R,8aR)-[(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine；(4aS,7S,8aR)-tetrahydro-8,8-dimethoxy-9,9-dimethyl-4H-4a,7-methanooxazirino[3,2-i][2,1]benzisothiazole 3,3-dioxide；(+)-[8,8-(dimethylcamphoryl)sulfonyl]oxaziridine；Davis reagent；(1S,6R,8S)-7,7-dimethoxy-11,11-dimethyl-5-oxa-3lambda6-thia-4-azatetracyclo[6.2.1.01,6.04,6]undecane 3,3-dioxide；(1S,6R,8S)-7,7-dimethoxy-11,11-dimethyl-5-oxa-3λ6-thia-4-azatetracyclo[6.2.1.01,6.04,6]undecane 3,3-dioxide
• CAS: 131863-82-6
• 化学式: C₁₂H₁₉NO₅S
• 分子量: 289.353
• InChiKey: LPZGAENGBPSMIO-MQSSHQKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  76.5
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-ethyl-5,8-dimethoxy-1,2,3,4-tetrahydronaphthalene-1-one 、 戴维斯试剂 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以66%的产率得到(-)-(R)-2-ethyl-5,8-dimethoxy-2-hydroxy-1,2,3,4-tetrahydronaphthalen-1-one
  参考文献：
  名称：

  Chemistry of oxaziridines. 16. A short, highly enantioselective synthesis of the AB-ring segments of .gamma.-rhodomycionone and .alpha.-citromycinone using (+)-[(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine

  摘要：

  A highly efficient procedure for the preparation of rhodomycinone 1 AB synthons (-)-2a and (+)-2b in high enantiomeric purity (93-4% ee) and good yield is described. This method involves asymmetric oxidation of the lithium enolate of 2-ethyl-5,8-dimethoxy-1-tetralone (4) with (+)-[(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine (5c), a new enantiomerically pure, aprotic oxidizing reagent. Lower stereoselectivities were observed with this reagent for the enantioselective oxidation of 2-substituted 1-tetralone enolates 8 lacking the 8-methoxy group.

  DOI：

  10.1021/jo00003a042
• 作为产物：
  描述：

  (+/-)-8,8-dimethyl-4,5,6,7-tetrahydro-3ar,6c-methano-benz[c]isothiazole-2,2-dioxide 在 selenium(IV) oxide 、 amberlyst-15 、 硫酸 、 potassium carbonate 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 、 水 、 溶剂黄146 为溶剂， 反应 28.0h， 生成 戴维斯试剂
  参考文献：
  名称：

  Chemistry of oxaziridines. 16. A short, highly enantioselective synthesis of the AB-ring segments of .gamma.-rhodomycionone and .alpha.-citromycinone using (+)-[(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine

  摘要：

  A highly efficient procedure for the preparation of rhodomycinone 1 AB synthons (-)-2a and (+)-2b in high enantiomeric purity (93-4% ee) and good yield is described. This method involves asymmetric oxidation of the lithium enolate of 2-ethyl-5,8-dimethoxy-1-tetralone (4) with (+)-[(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine (5c), a new enantiomerically pure, aprotic oxidizing reagent. Lower stereoselectivities were observed with this reagent for the enantioselective oxidation of 2-substituted 1-tetralone enolates 8 lacking the 8-methoxy group.

  DOI：

  10.1021/jo00003a042
• 作为试剂：
  描述：

  Methyl 5,8-dimethoxy-1,2,3,4-tetrahydro-2-naphthoate 在 双(三甲基硅烷基)氨基钾 、 戴维斯试剂 作用下， 生成 (S)-(-)-Methyl 2-hydroxy-5,8-dimethoxy-1-oxo-1,2,3,4-tetrahydro-2-naphthoate
  参考文献：
  名称：

  Asymmetric Synthesis of the AB Ring Segments of Daunomycin and 4-Demethoxydaunomycin

  摘要：

  Asymmetric hydroxylation of the potassium enolate of beta-keto ester 14, with (camphorsulfonyl)-oxaziridine (-)-7c [tetrahydro-9,9-dimethyl-8,8-dimethorry-4H-4a,7-methanooxazirino[3,2-i][2,1]-benzisothiazole 3,3-dioxide] affords alpha-hydroxy beta-keto ester (R)-(+)-15 in >95% ee. The high ee's are attributed to the fact that this enolate probably exists in one geometric form as a consequence of intramolecular chelation. Reduction of the ketone in 15 with triethylsilane and conversion of the ester group into the methyl ketone results in a highly efficient synthesis of the AB ring building block (R)-(-)-2-acetyl-5,8-dimethoxy-1,2,3,4-tetrahydro-2-napthol (3b), a key intermediate in the asymmetric synthesis of the antitumor agent 4-demethoxydaunomycin (1c). Selective deprotection of the 8-methoxy group in 3b with BBr3 gives 3a, important in the enantioselective synthesis of the clinically useful antitumor agent adriamycin (1b). Attempts to prepare 3a and 3b more directly by asymmetric hydroxylation of the enolates of methyl 5,8-dimethoxy-1,2,3,4-tetrahydro-2-naphthoate (9) or the 8-benzyloxy derivative of 16 resulted in low ee's, attributable to the formation of E/Z enolate mixtures and increased steric congestion in the transition state for hydroxylation.

  DOI：

  10.1021/jo00084a042

文献信息

• Asymmetric sulfoxidation using [(3,3-Dimethoxycamphoryl)sulfonyl]oxaziridine
  作者：Philip C. Bulman Page、Jag P. Heer、Donald Bethell、Eric W. Collington、David M. Andrews

  DOI：10.1016/0957-4166(95)00384-3

  日期：1995.12
• Camarero, Cristina; Arrasate, Sonia; Sotomayor, Nuria, ARKIVOC, 2010, vol. 2010, # 3, p. 45 - 55
  作者：Camarero, Cristina、Arrasate, Sonia、Sotomayor, Nuria、Lete, Esther

  DOI：——

  日期：——
• A highly enantioselective synthesis of (R)- and (S)-5,7-odimethyleucomol
  作者：Franklin A. Davis、Bang-Chi Chen

  DOI：10.1016/s0040-4039(00)97181-8

  日期：1990.1
• DAVIS, FRANKLIN A.;KUMAR, ANIL;CHEN, BANG-CHI, J. ORG. CHEM., 56,(1991) N, C. 1143-1145
  作者：DAVIS, FRANKLIN A.、KUMAR, ANIL、CHEN, BANG-CHI

  DOI：——

  日期：——
• Chemistry of oxaziridines. 16. A short, highly enantioselective synthesis of the AB-ring segments of .gamma.-rhodomycionone and .alpha.-citromycinone using (+)-[(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine
  作者：Franklin A. Davis、Anil Kumar、Bang Chi Chen

  DOI：10.1021/jo00003a042

  日期：1991.2

  A highly efficient procedure for the preparation of rhodomycinone 1 AB synthons (-)-2a and (+)-2b in high enantiomeric purity (93-4% ee) and good yield is described. This method involves asymmetric oxidation of the lithium enolate of 2-ethyl-5,8-dimethoxy-1-tetralone (4) with (+)-[(8,8-dimethoxycamphoryl)sulfonyl]oxaziridine (5c), a new enantiomerically pure, aprotic oxidizing reagent. Lower stereoselectivities were observed with this reagent for the enantioselective oxidation of 2-substituted 1-tetralone enolates 8 lacking the 8-methoxy group.