9-(4-nitro-benzenesulfonyl)-1,4-dihydro-1,4-epiazano-naphthalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 9-(4-nitro-benzenesulfonyl)-1,4-dihydro-1,4-epiazano-naphthalene
• 英文别名: 9-((4-nitrophenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene；(1R,8S)-11-(4-nitrophenyl)sulfonyl-11-azatricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraene
• 化学式: C₁₆H₁₂N₂O₄S
• 分子量: 328.348
• InChiKey: QBEUZZOFAZMMBU-IYBDPMFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  91.6
• 氢给体数：
  0
• 氢受体数：
  5

上下游信息

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	N-[(1R,2R)-2-(4-chlorophenoxy)-1,2-dihydronaphthalen-1-yl]-4-nitrobenzenesulfonamide	1370461-33-8	C22H17ClN2O5S	456.906
  ——	(1R,2R)-N-(2-(4-bromobenzyloxy)-1,2-dihydronaphthalen-1-yl)-4-nitrobenzenesulfonamide	1447061-26-8	C23H19BrN2O5S	515.384
  ——	(1R,2R)-N-(2-(benzo[d][1,3]dioxol-5-ylmethoxy)-1,2-dihydronaphthalen-1-yl)-4-nitrobenzenesulfonamide	1447061-33-7	C24H20N2O7S	480.498

反应信息

• 作为反应物：
  描述：

  9-(4-nitro-benzenesulfonyl)-1,4-dihydro-1,4-epiazano-naphthalene 、 3-氯苯酚 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 silver trifluoromethanesulfonate 、 四丁基碘化铵 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 四氢呋喃 为溶剂， 反应 64.0h， 以69%的产率得到
  参考文献：
  名称：

  铱催化含苯酚的氮杂双环烯烃的不对称开环

  摘要：

  使用由2.5 mol％的[Ir（COD）Cl] 2和5.0 mol％的（S）-BINAP原位生成的铱催化剂研究了氮杂双环烯烃与各种酚的不对称开环1,2-反式苯氧基氨基产物，收率极好（高达92％），对映选择性中等（良好）（高达ee高达98％）。通过X射线晶体学证实了产物4b的反式构型。

  DOI：

  10.1021/om3000295
• 作为产物：
  描述：

  N-Boc-7-azabenzobicyclo[2.2.1]heptadiene 、 对硝基苯磺酰氯 在 碘代三甲硅烷 、 三乙胺 、 甲醇 作用下， 以 二氯甲烷 为溶剂， 反应 1.42h， 以92%的产率得到9-(4-nitro-benzenesulfonyl)-1,4-dihydro-1,4-epiazano-naphthalene
  参考文献：
  名称：

  An Expedient Enantioselective Route to Diaminotetralins:  Application in the Preparation of Analgesic Compounds

  摘要：

  [GRAPHICS]Advances to the rhodium-catalyzed asymmetric ring-opening protocol have allowed this methodology to be extended to azabicyclic alkenes, the first time that rhodium has been used in allylic functionalizations with nitrogen leaving groups. The product diaminotetralins are important medicinal compounds. The synthetic utility of this methodology has been demonstrated in the total synthesis of an analgesic compound where the tetralin core, the regiochemistry, and the relative and absolute stereochemistry are all established in the ring-opening step.

  DOI：

  10.1021/ol026579i

文献信息

• Rhodium‐Catalyzed Enantioselective Oxidative [3+2] Annulation of Arenes and Azabicyclic Olefins through Twofold C−H Activation
  作者：Ruijie Mi、Guangfan Zheng、Zisong Qi、Xingwei Li

  DOI：10.1002/anie.201911086

  日期：2019.12.2

  mostly limited to ortho selectivity. Activation of both ortho and meta C-H bonds constitutes a particularly important strategy for annulation, but has rarely been studied in enantioselective systems. Reported herein is rhodium(III)-catalyzed asymmetric [3+2] transannulation of arenes with 7-azabenzonorbornadienes. Two distinct classes of arenes have been identified as substrates, and the coupling proceeded

  CH键的活化主要限于邻位选择性。邻位和间位CH键的激活都构成了特别重要的环空策略，但很少在对映选择性系统中进行研究。本文报道的是铑（III）催化的芳烃与7-氮杂苯并降冰片二烯的不对称[3 + 2]转环。已经鉴定出两种不同类型的芳烃作为底物，并且通过顺序激活邻位和间位CH键，以高对映选择性和优异的非对映选择性进行偶联。
• Iridium-catalyzed asymmetric ring-opening of azabicyclic alkenes with alcohols
  作者：Dingqiao Yang、Jiuyun Xia、Yuhua Long、Zhongyi Zeng、Xiongjun Zuo、Sanyong Wang、Chunrong Li

  DOI：10.1039/c3ob40891d

  日期：——

  A novel asymmetric ring-opening reaction of N-substituted azabenzonorbornadienes with a wide variety of substituted benzyl alcohols and the addition reaction of N-substituted azabenzonorbornadienes with thiols are reported, affording the corresponding 1,2-trans-alkoxyamino products in moderate yields with excellent enantioselectivities (up to 94% ee) and the corresponding thiol addition products in high yields with lower enantiomeric excesses (ee) in the presence of iridium catalyst, respectively. The effects of ligands, catalyst loading, solvents and additives, and temperature were also investigated. The anti-configuration of the product 3c was confirmed by X-ray crystal structure analysis. A possible mechanism for the present catalytic reaction is proposed.

  报道了一种新颖的N取代氮杂苯并双环烯的非对称开环反应，使用了多种取代苄醇，以及N取代氮杂苯并双环烯与硫醇的加成反应，分别获得了相应的1,2-trans-烷氧基氨基产物，产率适中且手性选择性优异（高达94% ee），以及在铱催化剂存在下高产率的相应硫醇加成产物，但手性过量（ee）较低。此外，还研究了配体、催化剂用量、溶剂和添加剂及温度的影响。通过X射线晶体结构分析确认了产物3c的反反式构型。提出了一种可能的催化反应机制。
• Rhodium(I)-Catalyzed Domino Asymmetric Ring Opening/Enantioselective Isomerization of Oxabicyclic Alkenes with Water
  作者：Gavin C. Tsui、Mark Lautens

  DOI：10.1002/anie.201200390

  日期：2012.5.29

  Water‐induced asymmetric ring opening: Enantio‐enriched 2‐hydroxy‐1‐tetralones are formed from oxabicyclic alkenes through a novel RhI‐catalyzed domino reaction. The proposed mechanism involves water‐induced asymmetric ring opening to generate chiral trans‐1,2‐diol intermediates and subsequent enantioselective isomerization (see scheme).

  水诱导的不对称开环：富含对映体的2-羟基-1-四氢萘酮是由氧杂双环烯烃通过新颖的Rh I催化的多米诺反应形成的。拟议的机制涉及水诱导的不对称开环，以产生手性反式-1，2-二醇中间体，以及随后的对映选择性异构化（参见方案）。
• Iridium/copper-cocatalyzed asymmetric ring opening reaction of azabenzonorbornadienes with amines
  作者：Chaoyuan Zeng、Fan Yang、Jingchao Chen、Jun Wang、Baomin Fan

  DOI：10.1039/c5ob01243k

  日期：——

  A combination of iridium/copper associated with (R)-Difluorphos catalyst for the asymmetric ring opening reaction of azabenzonorbornadienes with amines was developed, which afforded chiral trans-vicinal diamines in 80–97% yields with 93–95% enantioselectivities.

  开发了铱/铜与（R）-二氟膦催化剂的结合物，用于氮杂苯并降冰片二烯与胺的不对称开环反应，可提供手性反式邻位二胺，产率为80-97％，对映选择性为93-95％。
• Palladium-Catalyzed Asymmetric Ring Opening Reaction of Azabenzonorbornadienes with Aromatic Amines
  作者：Zhiwu Lu、Jun Wang、Baiqiu Han、Sifeng Li、Yongyun Zhou、Baomin Fan

  DOI：10.1002/adsc.201500530

  日期：2015.10.12

  palladium/(R)-Binap catalyst for asymmetric ring opening reaction of azabenzonorbornadienes with amines was developed that afforded the corresponding substituted dihydronaphthalenes in good yields (up to 97%) with excellent enantioselectivities (up to >99% ee). To the best of our knowledge, this represents the first palladium-catalyzed asymmetric ring opening reaction of azabenzonorbornadienes with heteronucleophiles

  开发了用于氮杂苯并降冰片二烯与胺的不对称开环反应的钯/（R）-Binap催化剂，该催化剂以良好的对映选择性（高达99％ee）以良好的收率（高达97％）提供了相应的取代二氢萘。据我们所知，这是氮杂苯并降冰片二烯与杂亲核试剂的第一个钯催化的不对称开环反应。