<(2,4-dinitrophenylsulfonyl)imino>phenyl-λ³-iodane | 181306-54-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: <(2,4-dinitrophenylsulfonyl)imino>phenyl-λ³-iodane
• 英文别名: [(2,4-dinitrophenylsulfonyl)imino]phenyliodinane；DNsN=IPh；2,4-dinitro-N-(phenyl-lambda3-iodanylidene)benzenesulfonamide；2,4-dinitro-N-(phenyl-λ3-iodanylidene)benzenesulfonamide
• CAS: 181306-54-7
• 化学式: C₁₂H₈IN₃O₆S
• 分子量: 449.183
• InChiKey: FIFTVZZQCXZORC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  147
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  苯乙烯 、 <(2,4-dinitrophenylsulfonyl)imino>phenyl-λ³-iodane 在 copper acetylacetonate 作用下， 以 乙腈 为溶剂， 反应 1.67h， 以58%的产率得到(N-2,4-dinitrohenylsulfonyl)-2-phenylaziridine
  参考文献：
  名称：

  Rhodium(II)-catalyzed aziridinations and CH insertions with [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane

  摘要：

  The [Rh-2(OAc)(4)]-catalyzed decomposition of NsN=IPh {[N-(p-nitrobenzenesulfonyl)imino]phenyliodinane} in the presence of olefins affords aziridines in yields of up to 85%. The aziridination of cis-hex-2-ene and cis-beta- methylstyrene is stereospecific, but, cis-stilbene affords a 3:1 mixture of cis- and trans-aziridines in low yield. With chiral Rh(II) catalysts, optically active aziridines are formed having enantiomeric excesses of up to 73%. The NsN=IPh-[Rh-2(OAc)(4)] system is also efficient for the allylic amination of olefins and for insertion into CH bonds, activated by phenyl or oxygen substituents.

  DOI：

  10.1002/(sici)1099-1395(199606)9:6<341::aid-poc791>3.0.co;2-5
• 作为产物：
  描述：

  碘苯二乙酸 、 2,4-二硝基苯磺酰胺 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 <(2,4-dinitrophenylsulfonyl)imino>phenyl-λ³-iodane
  参考文献：
  名称：

  The rhodium(II)-catalyzed aziridination of olefins with {[(4-nitrophenyl)sulfonyl]imino}phenyl-lambda³-iodane

  摘要：

  The aziridination of olefins with {(4-nitrophenylsulfonyl)imino)phenyl-lambda(3)-iodane, NsN=IPh (1c), in the presence of [Rh-2(OAc)(4)] proceeds in yields of up to 85% when the olefin is used in large excess. Under optimized conditions, styrene (4a) is aziridinated with 1 equiv. of NsN=IPh (1c) in 64% yield with 2 mol% of catalyst. The aziridines derived from electron-rich olefins undergo ring-opening under the conditions of the aziridination and afford rearrangement products or pyrrolidines. The aziridination is sterospecific with 1,2-dialkyl- and 1,2-arylalkyl-disubstituted olefins, but nonstereospecific with stilbene. The rho-value for aziridination of substituted styrenes is -0.61. No ring-opened products are observed upon aziridination of vinylcyclopropanes. Tn the presence of chiral Rh-II catalysts, the aziridination is enantioselective, affording an ee of 73% with cis-beta-methylstyrene (4k) and Pirrungs [Rh-2{(R)-(-)-bnp}(4)] catalyst. The experimental results are consistent with a one-step mechanism for transfer of the nitrenoid moiety from the catalyst to the olefin.

  DOI：

  10.1139/cjc-76-6-738

文献信息

• Asymmetric formal synthesis of (−)-pancracine via catalytic enantioselective C–H amination process
  作者：Masahiro Anada、Masahiko Tanaka、Naoyuki Shimada、Hisanori Nambu、Minoru Yamawaki、Shunichi Hashimoto

  DOI：10.1016/j.tet.2008.10.091

  日期：2009.4

  reaction of silyl enol ethers derived from cyclohexanone with [(4-nitrophenylsulfonyl)imino]phenyliodinane (pNsNIPh) catalyzed by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh2(S-TCPTTL)4, provides, after desilylation, N-pNs-protected (S)-β-aminocyclohexanone in up to 72% ee. This represents the first example of the insertion of nitrene species into an allylic C–H bond of silyl enol

  的反应的甲硅烷基烯醇醚由环己酮衍生自具有[（4-硝基苯基磺酰基）亚氨基] phenyliodinane（p NSN IPH）由二铑（II）催化的四[ Ñ -tetrachlorophthaloyl-（小号） -叔-leucinate]的Rh 2（小号- TCPTTL）4，在去甲硅烷基化后提供受N - p Ns保护的（S）-β-氨基环己酮的ee含量高达72％。这代表了将氮烯类插入甲硅烷基烯醇醚的烯丙基CH键中的第一个例子。使用该方法，已经开发出一种新的催化不对称路线，该路线通往Overman合成单宁类金盏花生物碱（-）-Pancracine的高级中间体。关键步骤涉及（a）一锅Rh 2（R -TCPTTL）4催化的2-环己烯-1-酮的连续1,4-氢化硅烷化/对映选择性C–H胺化，（b）N-烷基化及随后的反应分子内的Mukaiyama aldol反应/脱水，以及（c）双环烯酮的区域和立体控制的还原性脱氧27与双键的迁移，以建立C1
• [EN] SYSTEM FOR FLUORINATING ORGANIC COMPOUNDS<br/>[FR] SYSTÈME DE FLUORATION DE COMPOSÉS ORGANIQUES
  申请人：HARVARD COLLEGE

  公开号：WO2009100014A1

  公开（公告）日：2009-08-13

  Described herein are fluorinated organic compounds and methods of making fluorinated organic compounds, for example, using palladium complexes. Also described herein are compositions and kits containing compounds and palladium complexes described herein.

  本文描述了氟化有机化合物及制备氟化有机化合物的方法，例如使用钯配合物。本文还描述了含有上述化合物和钯配合物的组合物和试剂盒。
• Catalytic Enantioselective Amination of Silyl Enol Ethers Using Chiral Dirhodium(II) Carboxylates:  Asymmetric Formal Synthesis of (−)-Metazocine
  作者：Masahiro Anada、Masahiko Tanaka、Takuya Washio、Minoru Yamawaki、Takumi Abe、Shunichi Hashimoto

  DOI：10.1021/ol702019b

  日期：2007.10.1

  catalyst for enantioselective aminations of silyl enol ethers derived from acyclic ketones or alpha,beta-enones with [N-(2-nitrophenylsulfonyl)imino]phenyliodinane (NsN=IPh), providing N-(2-nitrophenylsulfonyl)-alpha-amino ketones in high yields and with enantioselectivities of up to 95% ee. The effectiveness of the present catalytic protocol has been demonstrated by an asymmetric formal synthesis of (-)-metazocine

  四[N-四氟邻苯二甲酰基-（S）-叔亮氨酸酯]铑（II）Rh2（S-TFPTTL）4是一种非常有效的催化剂，用于衍生自无环酮或α，β-烯酮的甲硅烷基烯醇醚的对映选择性胺化[N-（2-硝基苯基磺酰基）亚氨基]苯基碘丁烷（NsN = IPh），可高收率提供N-（2-硝基苯基磺酰基）-α-氨基酮，对映选择性高达95％ee。本催化方案的有效性已通过（-）-甲磺酸的不对称形式合成证明。
• Desymmetrization ofN-Sulfonated Aziridines by Alkyllithium Reagents in the Presence of Chiral Ligands
  作者：Paul Müller、David Riegert、Gérald Bernardinelli

  DOI：10.1002/hlca.200490010

  日期：2004.1

  epoxides. Similarily, the allylic sulfonamide 10, resulting from rearrangement of 7-[(4-methylphenyl)sulfonyl]-7-azabicyclo[4.1.0]heptane (7) under the same reaction conditions, had the (R)-configuration, while cyclohexen-3-ol, obtained upon rearrangement of cyclohexene oxide, is known to be (S)-configured. Deuterium labelling showed that the rearrangement of 7 proceeds via enantioselective α-elimination

  所述的重新排列的立体化学过程Ñ -sulfonylaziridines 5,15，和25中的存在小号正丁基锂/（ - ） -鹰爪豆碱的二环磺胺4,16，和17，分别为已被化学和调查了X射线结构分析。在所有情况下，产物的绝对构型与在相应的环氧化物重排时形成的醇的绝对构型相反。类似地，在相同反应条件下，由7-[（4-甲基苯基）磺酰基] -7-氮杂双环[4.1.0]庚烷（7）的重排产生的烯丙基磺酰胺10具有（R）-构型，而通过环己烯氧化物的重排获得的环己烯-3-醇是已知的（S）-构型。氘标记表明的重排7个前进通过对映选择性α在剔除到卡宾，其经历1,2--H转变。
• SYSTEM FOR FLUORINATING ORGANIC COMPOUNDS
  申请人：Ritter Tobias

  公开号：US20110054175A1

  公开（公告）日：2011-03-03

  Described herein are fluorinated organic compounds and methods of making fluorinated organic compounds, for example, using palladium complexes. Also described herein are compositions and kits containing compounds and palladium complexes described herein.

  本文描述了含氟有机化合物及制备含氟有机化合物的方法，例如使用钯配合物。本文还描述了含有本文所述化合物和钯配合物的组合物和试剂盒。