(aR,4bS,7R)-6,7-dihydro-4b-methyl-7-phenyldibenz[c,e]oxazolo[3,2-a]azepin-9(4bH)-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: (aR,4bS,7R)-6,7-dihydro-4b-methyl-7-phenyldibenz[c,e]oxazolo[3,2-a]azepin-9(4bH)-one
• 英文别名: (2S,5R)-2-methyl-5-phenyl-3-oxa-6-azatetracyclo[12.4.0.02,6.08,13]octadeca-1(18),8,10,12,14,16-hexaen-7-one
• 化学式: C₂₃H₁₉NO₂
• 分子量: 341.409
• InChiKey: LLVPSNBBTLKFAX-GMAHTHKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (aR,4bS,7R)-6,7-dihydro-4b-methyl-7-phenyldibenz[c,e]oxazolo[3,2-a]azepin-9(4bH)-one 在 aluminum (III) chloride 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以87%的产率得到(R)-2-((5R)-5-methyl-5H-dibenzo[c,e]azepin-6(7H)-yl)-2-phenylethanol
  参考文献：
  名称：

  对5-甲基和5,7-二甲基-6,7-二氢-5 H-二苯并[ c，e ]氮杂的对映选择性路线：具有可转换的轴向手性的仲胺

  摘要：

  从2'-乙酰基联苯-2-羧酸对映体选择性地制备了一种新的具有轴心立体化学继电器的仲胺（-）-5-甲基-6,7-二氢-5 H-二苯并[ c，e ]氮杂4（R）-2-苯基甘醇作为辅助剂来控制两个手性元素。4中的联芳基轴优先采用a S-构型，且甲基取代基为伪赤道形式，但如根据分子力学计算所预测的，转化成相应的N -Boc衍生物会将其锁定为a R-构型。

  DOI：

  10.1021/ol900333c
• 作为产物：
  描述：

  2-碘苯甲酸乙酯, 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 186.0h， 生成 (aR,4bS,7R)-6,7-dihydro-4b-methyl-7-phenyldibenz[c,e]oxazolo[3,2-a]azepin-9(4bH)-one
  参考文献：
  名称：

  Novel Extension of Meyers' Methodology:  Stereoselective Construction of Axially Chiral 7,5-Fused Bicyclic Lactams

  摘要：

  A novel extension of Meyer's lactamization is reported for the preparation of seven-membered ring lactams 1a-d incorporating a biaryl unit. The required keto-esters 2a-c were readily accessible via the Suzuki coupling reaction. A borylation-Suzuki coupling (BSC) sequence was successfully developed for the high-yielding preparation of keto-ester 2d. Cyclization of the resulting keto-esters 2a-d or keto-acids 5a,c,d in the presence of (R)-phenylglycinol afforded the desired lactams 1a-d in high yields (72-93%) and excellent diastereoselectivities (>95%). This methodology provides a facile stereoselective access to new axially chiral bridged biaryls.

  DOI：

  10.1021/jo035195i

文献信息

• Developments in Meyers’ Lactamization Methodology: En Route to Bi(hetero)aryl Structures with Defined Axial Chirality
  作者：Svetlana Postikova、Mohamad Sabbah、Daniel Wightman、Ich Tuan Nguyen、Morgane Sanselme、Thierry Besson、Jean-François Brière、Sylvain Oudeyer、Vincent Levacher

  DOI：10.1021/jo401259w

  日期：2013.8.16

  Highly atroposelective Meyers' lactamization promoted by pivalic acid under microwave irradiation is reported which allows the construction of nonracemic substituted-dibenzo(di)azepine derivatives through a center to axial chirality transfer principle, controlling the otherwise configurationally labile biaryl axis. This approach provides a straightforward entry to enantioenriched analogues of biorelevant architectures.
• Novel Extension of Meyers' Methodology:  Stereoselective Construction of Axially Chiral 7,5-Fused Bicyclic Lactams
  作者：Maël Penhoat、Vincent Levacher、Georges Dupas

  DOI：10.1021/jo035195i

  日期：2003.11.1

  A novel extension of Meyer's lactamization is reported for the preparation of seven-membered ring lactams 1a-d incorporating a biaryl unit. The required keto-esters 2a-c were readily accessible via the Suzuki coupling reaction. A borylation-Suzuki coupling (BSC) sequence was successfully developed for the high-yielding preparation of keto-ester 2d. Cyclization of the resulting keto-esters 2a-d or keto-acids 5a,c,d in the presence of (R)-phenylglycinol afforded the desired lactams 1a-d in high yields (72-93%) and excellent diastereoselectivities (>95%). This methodology provides a facile stereoselective access to new axially chiral bridged biaryls.
• Enantioselective Route to 5-Methyl- and 5,7-Dimethyl-6,7-dihydro-5<i>H</i>-dibenz[<i>c</i>,<i>e</i>]azepine: Secondary Amines with Switchable Axial Chirality
  作者：Silvain L. Pira、Timothy W. Wallace、Jonathan P. Graham

  DOI：10.1021/ol900333c

  日期：2009.4.2

  featuring an axis-center stereochemical relay, was prepared enantioselectively from 2′-acetylbiphenyl-2-carboxylic acid, using (R)-2-phenylglycinol as an auxiliary for the control of both elements of chirality. The biaryl axis in 4 preferentially adopts the aS-configuration, with the methyl substituent pseudoequatorial, but conversion into the corresponding N-Boc derivative locks the axis into the aR-configuration

  从2'-乙酰基联苯-2-羧酸对映体选择性地制备了一种新的具有轴心立体化学继电器的仲胺（-）-5-甲基-6,7-二氢-5 H-二苯并[ c，e ]氮杂4（R）-2-苯基甘醇作为辅助剂来控制两个手性元素。4中的联芳基轴优先采用a S-构型，且甲基取代基为伪赤道形式，但如根据分子力学计算所预测的，转化成相应的N -Boc衍生物会将其锁定为a R-构型。