3-methyl-3,6-dihydro-[1,2]oxazine-2-carboxylic acid tert-butyl ester

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环化合物
• 英文名称: 3-methyl-3,6-dihydro-[1,2]oxazine-2-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl 3-methyl-3,6-dihydro-2H-1,2-oxazine-2-carboxylate；Tert-butyl 3-methyl-3,6-dihydrooxazine-2-carboxylate
• 化学式: C₁₀H₁₇NO₃
• 分子量: 199.25
• InChiKey: ROAQKCSRXDLXSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  间戊二烯 、 N-羟基氨基甲酸叔丁酯 在 叔丁基过氧化氢 、 dirhodium(II) caprolactamate bis(acetonitrile) 作用下， 以 癸烷 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 6-methyl-3,6-dihydro-[1,2]oxazine-2-carboxylic acid tert-butyl ester 、 3-methyl-3,6-dihydro-[1,2]oxazine-2-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  The Oxidative Acylnitroso Hetero-Diels-Alder Reaction Catalyzed by Dirhodium Caprolactamate

  摘要：

  An effective protocol is described for the generation and in situ Diels-Alder trapping of acylnitroso derivatives. In this procedure, the oxidation of hydroxamic acid is efficiently catalyzed by dirhodium(II) caprolactamate with tert-butyl hydroperoxide (TBHP) in the presence of dienes at room temperature. Using this approach we obtained a variety of hetero-Diels-Alder cycloadducts in yields of up to 96% at 0.1 mol% catalyst loading.

  DOI：

  10.1055/s-0031-1289786

文献信息

• The development and application of ruthenium catalysed oxidations of a hydroxamic acid and in situ Diels–Alder trapping of the acyl nitroso derivative
  作者：Kevin R. Flower、Andrew P. Lightfoot、Hayley Wan、Andrew Whiting

  DOI：10.1039/b206430h

  日期：——

  11%). Ruthenium( II) salen complexes also catalyse the oxidation of N-Boc-hydroxylamine in the presence of TBHP, to give the N-Boc-nitroso compound which can be efficiently trapped with a range of dienes. However, use of an enantiopure ruthenium salen complex does not produce asymmetric induction via the trapping of the intermediate acyl nitroso dienophile with cyclohexadiene, which strongly suggests

  钌（ II）配合物可用于氧化 N -Boc-羟胺 在......的存在下 叔丁基过氧化氢 （TBHP）转化为相应的亚硝基双亲物， 环己-1,3-二烯作为杂Diels–Alder加合物。已经获得了直接干预的证据。三苯基氧化膦稳定的钌（ IV）氧代-络合物作为催化活性物质。手性双齿双膦衍生钌的用途配体（BINAP或PROPHOS）导致极低的不对称感应（8％和11％）。钌（ II）沙伦络合物还可以在TBHP存在下催化N -Boc-羟胺的氧化 ，得到 N -Boc-亚硝基化合物，该化合物可以有效地被一系列二烯捕获。但是，使用对映纯的钌salen配合物不会通过捕获中间体而产生不对称感应 酰基 亚硝基亲二烯体与 环己二烯，这强烈表明中间体在Diels–Alder环加成之前很容易从参与氧化步骤的手性钌络合物中解离。
• Generation of Acylnitroso Dienophiles:  A Study of Metal Catalysis
  作者：Mauro F. A. Adamo、Simone Bruschi

  DOI：10.1021/jo062334y

  日期：2007.3.1

  [GRAPHIC]Four novel metal/amine catalysts efficiently converted Boc-NHOH to its acylnitroso species at 5 mol % catalyst loading. These reactions allowed the preparation of polyfunctional hetero Diels-Alder adducts in high yield and from truly commercially available materials.
• The Oxidative Acylnitroso Hetero-Diels-Alder Reaction Catalyzed by Dirhodium Caprolactamate
  作者：Chong-Dao Lu、Xiarepati Tusun

  DOI：10.1055/s-0031-1289786

  日期：2012.7

  An effective protocol is described for the generation and in situ Diels-Alder trapping of acylnitroso derivatives. In this procedure, the oxidation of hydroxamic acid is efficiently catalyzed by dirhodium(II) caprolactamate with tert-butyl hydroperoxide (TBHP) in the presence of dienes at room temperature. Using this approach we obtained a variety of hetero-Diels-Alder cycloadducts in yields of up to 96% at 0.1 mol% catalyst loading.