(S,Z)-methyl 3-(tert-butyldimethylsilyloxy)-4-((S)-1,4-dihydronaphthalen-1-yl)pent-2-enoate | 1217534-80-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S,Z)-methyl 3-(tert-butyldimethylsilyloxy)-4-((S)-1,4-dihydronaphthalen-1-yl)pent-2-enoate
• 英文别名: methyl (Z,4S)-3-[tert-butyl(dimethyl)silyl]oxy-4-[(1S)-1,4-dihydronaphthalen-1-yl]pent-2-enoate
• CAS: 1217534-80-9
• 化学式: C₂₂H₃₂O₃Si
• 分子量: 372.58
• InChiKey: ISDCAKZACIUYHN-PNNGTBSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1,2-二氢萘 、 (Z)-methyl 3-(tert-butyldimethylsilyloxy)-2-diazopent-3-enoate 在 Rh₂(S-PTAD)4 作用下， 以 2,2-二甲基丁烷 为溶剂， 反应 18.0h， 生成 (R,Z)-methyl 3-(tert-butyldimethylsilyloxy)-4-((R)-1,4-dihydronaphthalen-1-yl)pent-2-enoate 、 (S,Z)-methyl 3-(tert-butyldimethylsilyloxy)-4-((S)-1,4-dihydronaphthalen-1-yl)pent-2-enoate 、 (1R,1aS,7bS)-methyl 1-((Z)-1-(tert-butyldimethylsilyloxy)prop-1-enyl)-1a,2,3,7b-tetrahydro-1H-cyclopropa[a]naphthalene-1-carboxylate
  参考文献：
  名称：

  Controlling Factors for C−H Functionalization versus Cyclopropanation of Dihydronaphthalenes

  摘要：

  Rhodium(II)-catalyzed reactions of vinyldiazoacetates with dihydronaphthalenes were systematically studied. These substrates underwent cyclopropanantion and/or the combined C-H activation/Cope rearrangement in good overall yield and with good diastereo- and enantiocontrol. The selectivity of these reactions was profoundly influenced by the nature of the chiral catalyst, the vinyldiazoacetate, and the dihydronaphthalene. The best combinations for achieving the highest selectivity in the cyclopropanation and the combined C-H activation/Cope rearrangement of 1,2-dihydronaphthalenes are methyl 2-diazopent-3-enoate (2a)/Rh-2(S-DOSP)(4) and methyl 3-(tert-butyldimethylsilyloxy)-2-diazopent-3-enoate (2b)/Rh-2(S-PTAD)(4). These combinations are very effective at enantiodivergent reactions of 1-methyl-1,2-dihydronaphthalenes.

  DOI：

  10.1021/jo902644f

文献信息

• Controlling Factors for C−H Functionalization versus Cyclopropanation of Dihydronaphthalenes
  作者：Etienne Nadeau、Dominic L. Ventura、Jonathan A. Brekan、Huw M. L. Davies

  DOI：10.1021/jo902644f

  日期：2010.3.19

  Rhodium(II)-catalyzed reactions of vinyldiazoacetates with dihydronaphthalenes were systematically studied. These substrates underwent cyclopropanantion and/or the combined C-H activation/Cope rearrangement in good overall yield and with good diastereo- and enantiocontrol. The selectivity of these reactions was profoundly influenced by the nature of the chiral catalyst, the vinyldiazoacetate, and the dihydronaphthalene. The best combinations for achieving the highest selectivity in the cyclopropanation and the combined C-H activation/Cope rearrangement of 1,2-dihydronaphthalenes are methyl 2-diazopent-3-enoate (2a)/Rh-2(S-DOSP)(4) and methyl 3-(tert-butyldimethylsilyloxy)-2-diazopent-3-enoate (2b)/Rh-2(S-PTAD)(4). These combinations are very effective at enantiodivergent reactions of 1-methyl-1,2-dihydronaphthalenes.