benzyl N-[2-(dimethylamino)-2-oxoethyl]-N-[(1R,2R,2'R,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,6'-oxane]-2'-yl]carbamate | 810671-46-6

• 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
• 英文名称: benzyl N-[2-(dimethylamino)-2-oxoethyl]-N-[(1R,2R,2'R,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,6'-oxane]-2'-yl]carbamate
• CAS: 810671-46-6
• 化学式: C₂₆H₃₈N₂O₄
• 分子量: 442.599
• InChiKey: MWHLZNJNMDSMDN-SUVBRTNGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl N-[2-(dimethylamino)-2-oxoethyl]-N-[(1R,2R,2'R,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,6'-oxane]-2'-yl]carbamate 在 三氟乙酸 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 9.0h， 生成 ethyl (3S,4R)-5-(dimethylamino)-3-methyl-5-oxo-4-(phenylmethoxycarbonylamino)pentanoate
  参考文献：
  名称：

  CamTHP *不对称的甘氨酰胺的高度立体选择性Michael加成反应，用于合成功能密集的氨基酸衍生物。

  摘要：

  樟脑衍生的四氢吡喃（camTHP *）脱对称的甘氨酰胺1经过高效且高度非对映选择性的烯醇化锂，加入硝基烯烃，α，β-不饱和酮，酯和内酯中。这些产物的直接操作提供了3-取代的焦谷氨酰胺和β-芳基-α，γ-二氨基酸衍生物，突出了使用这种新型结构单元合成对映异构体富集，功能密集的分子的简便性。[反应：看文字]

  DOI：

  10.1021/ol048568q
• 作为产物：
  描述：

  (+/-)-2-allyl-1,7,7-trimethyl-norbornane-2exo-ol 在 dirhodium tetraacetate 、 4,5-bis(diphenylphosphino)-9,9-dimethyl xanthine 、 氢气 、 sodium carbonate 作用下， 以 乙醚 为溶剂， 120.0 ℃ 、5.0 MPa 条件下， 反应 16.0h， 生成 benzyl N-[2-(dimethylamino)-2-oxoethyl]-N-[(1R,2R,2'R,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,6'-oxane]-2'-yl]carbamate
  参考文献：
  名称：

  CamTHP*OH:  A Camphor-Derived δ-Lactol Auxiliary for the Effective Desymmetrization of Attached Glycinamide Residues. Asymmetric Synthesis of α-Amino Carbonyl Compounds

  摘要：

  Stereoselective allylation of camphor and subsequent terminal hydroformylation affords a new delta-lactol auxiliary (camTHP*OH) on multigram scale. Stereoselective condensation with glycine dimethylamide and Cbz protection affords a camTHP*-desymmetrized glycinamide building block which undergoes efficient and highly diastereoselective metal enolate alkylation reactions. Acid-mediated deprotection affords the N-Cbz-protected a-amino amide products which may be converted directly to alpha-amino ketones on treatment with Grignard or organolithium reagents without loss of stereochemical integrity.

  DOI：

  10.1021/ol048569i

文献信息

• CamTHP*OH:  A Camphor-Derived δ-Lactol Auxiliary for the Effective Desymmetrization of Attached Glycinamide Residues. Asymmetric Synthesis of α-Amino Carbonyl Compounds
  作者：Darren J. Dixon、Richard A. J. Horan、Nathaniel J. T. Monck

  DOI：10.1021/ol048569i

  日期：2004.11.1

  Stereoselective allylation of camphor and subsequent terminal hydroformylation affords a new delta-lactol auxiliary (camTHP*OH) on multigram scale. Stereoselective condensation with glycine dimethylamide and Cbz protection affords a camTHP*-desymmetrized glycinamide building block which undergoes efficient and highly diastereoselective metal enolate alkylation reactions. Acid-mediated deprotection affords the N-Cbz-protected a-amino amide products which may be converted directly to alpha-amino ketones on treatment with Grignard or organolithium reagents without loss of stereochemical integrity.
• Highly Stereoselective Michael Addition Reactions of CamTHP*-Desymmetrized Glycinamide for the Synthesis of Functionally Dense Amino Acid Derivatives
  作者：Darren J. Dixon、Richard A. J. Horan、Nathaniel J. T. Monck、Paul Berg

  DOI：10.1021/ol048568q

  日期：2004.11.1

  glycinamide 1 undergoes efficient and highly diastereoselective lithium enolate Michael additions to nitro olefins, alpha,beta-unsaturated ketones, esters, and lactones. Straightforward manipulation of these products affords 3-substituted pyroglutamides and beta-aryl-alpha,gamma-diamino acid derivatives, highlighting the ease of synthesis of enantiomerically enriched, functionally dense molecules using this novel

  樟脑衍生的四氢吡喃（camTHP *）脱对称的甘氨酰胺1经过高效且高度非对映选择性的烯醇化锂，加入硝基烯烃，α，β-不饱和酮，酯和内酯中。这些产物的直接操作提供了3-取代的焦谷氨酰胺和β-芳基-α，γ-二氨基酸衍生物，突出了使用这种新型结构单元合成对映异构体富集，功能密集的分子的简便性。[反应：看文字]