trans-N-Boc-7,9-dimethyl-1,4-dioxa-8-azaspiro<4.5>decane | 126503-27-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂螺癸烷衍生物
• 英文名称: trans-N-Boc-7,9-dimethyl-1,4-dioxa-8-azaspiro<4.5>decane
• 英文别名: tert-butyl (7S,9S)-7,9-dimethyl-1,4-dioxa-8-azaspiro[4.5]decane-8-carboxylate
• CAS: 126503-27-3
• 化学式: C₁₄H₂₅NO₄
• 分子量: 271.357
• InChiKey: KMBLRONJWRBHKI-QWRGUYRKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.54
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  48.0
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  trans-N-Boc-7,9-dimethyl-1,4-dioxa-8-azaspiro<4.5>decane 在 sodium tetrahydroborate 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.17h， 生成 (2R,6R)-REL-1-BOC-2,6-二甲基-4-羟基哌啶
  参考文献：
  名称：

  .alpha.-Lithioamine synthetic equivalents: syntheses of diastereoisomers from Boc derivatives of cyclic amines

  摘要：

  Sequences of alpha'-lithiations and electrophilic substitutions of Boc-pyrrolidines, Boc-piperidines, and Boc-hexahydroazepines that provide compounds which are substituted adjacent to nitrogen are reported, and the pathways of the reactions are discussed. By this methodology monosubstituted 2 and disubstituted 2,4,2,6, and 2,5 Boc-piperidines are obtained as single or separable diastereoisomers consistent with equatorial lithiations and retentive electrophilic substitution in chair conformations. Both cis and trans 2,6-disubstituted diastereoisomers can be prepared, and control of diastereoselectivity is demonstrated by syntheses of solenopsin A, a 2,6-trans-disubstituted piperidine, and of Boc-dihydropinidine, a 2,6-cis-disubstituted piperidine. In the case of 3-methoxy-Boc-piperidine elimination of methoxide occurs upon lithiation, and with cis-2,4-disubstituted Boc-piperidines the electrophile is introduced with trans stereochemistry at C-6. These reactions are suggested to involve twist boat conformations consistent with an X-ray crystal structure of 2-methyl-6-(trimethylstannyl)-4-phenyl-N-Boc-piperidine. Boc-pyrrolidine lithiates more rapidly than Boc-piperidine, provides 2-substituted products with electrophiles, and on further lithiation-substitution gives 2,5-cis- and -trans-substituted products. Boc-perhydroazepine provides 2-substituted products by the sequence and on further lithiation-substitution gives 2,7-trans-disubstituted products.

  DOI：

  10.1021/jo00057a024
• 作为产物：
  描述：

  4,4-(乙烯二氧基)-1-叔丁氧羰基哌啶 在 四甲基乙二胺 、 仲丁基锂 作用下， 生成 trans-N-Boc-7,9-dimethyl-1,4-dioxa-8-azaspiro<4.5>decane
  参考文献：
  名称：

  .alpha.-Lithioamine synthetic equivalents: syntheses of diastereoisomers from the Boc-piperidines

  摘要：

  DOI：

  10.1021/jo00296a008