N-(2,3-butadienyl)-4-methyl-N-(3-oxopropyl)benzenesulfonamide

• 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: N-(2,3-butadienyl)-4-methyl-N-(3-oxopropyl)benzenesulfonamide
• 化学式: C₁₄H₁₇NO₃S
• 分子量: 279.36
• InChiKey: BNPUDWWSBWBLAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  62.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(2,3-butadienyl)-4-methyl-N-(3-oxopropyl)benzenesulfonamide 在 titanium(IV) tetraethanolate 、 bis(η3-allyl-μ-chloropalladium(II)) 、 二乙二醇二甲醚 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 4.0h， 生成 (+)-(S)-2-methyl-N-[(3S,4R)-1-tosyl-3-{1-(trimethylstannyl)vinyl}-piperidin-4-yl]propane-2-sulfinamide
  参考文献：
  名称：

  Regulation of Diastereoselectivity in the Carbocyclization of Allenyl (S)-N-tert-Butylsulfinimines through a Three-Component Assembly

  摘要：

  Allenyl sulfinimines can be stereoselectively cyclized with hexamethylditin under palladium catalysis conditions followed by a selection of additives for an activated transmetalation. Reactivity and diastereoselectivity for the cyclization strongly depend on the characteristics of additives. A highly diastereoselective synthesis of five-membered rings is achieved from the reaction of the corresponding allenyl (5)-N-tert-butylsulfinimies through the following sequence. After the distannylation of the allenyl group with hexamethylditin catalyzed by the Pd complex, stereochemical routes are additive dependent: addition of SnCl4 affords a cis ring exclusively, whereas a trans ring is formed predominantly by the introduction of B-bromocatecholborane. Extension of the methodology to the synthesis of six-membered cis rings is achieved by using B-bromocatecholborane. Stereochemical relationships of products were unambiguously deduced by X-ray crystallography.

  DOI：

  10.1021/jo4025072

文献信息

• Key Factors for High Diastereo- and Enantioselectivity of Umpolung Cyclizations of Aldehyde-Containing Allylpalladium Intermediates
  作者：Hirokazu Tsukamoto、Ayumu Kawase、Hirotaka Omura、Takayuki Doi

  DOI：10.1246/bcsj.20190167

  日期：2019.10.15

  Two palladium/chiral diphosphine-catalyzed umpolung cyclizations of aldehyde-containing allylic acetates and allenes with arylboronic acid are fully investigated to establish key factors in their h...

  充分研究了两种钯/手性二膦催化的含醛乙酸烯丙酯和丙二烯与芳基硼酸的 umpolung 环化反应，以确定其反应的关键因素。
• Platinum(II)-Catalyzed Allylation of CO and CN Bonds under Hydrogenation Conditions
  作者：Jong-Tai Hong、Xi Wang、Ji-Hwan Kim、Kyunghee Kim、Hoseop Yun、Hye-Young Jang

  DOI：10.1002/adsc.201000648

  日期：2010.11.22

  nucleophilic addition of allylplatinum to a range of electrophiles including carbonyls, oximes, and hydrazones was examined. Platinum(II) catalysts and allene substrates were subject to hydrogenation conditions to generate nucleophilic allylplatinum complexes without using a stoichiometric amount of toxic and sensitive organometallic reagents. The allylplatinum intermediates reacted with CO and CN bonds to produce

  研究了烯丙基铂在包括羰基，肟和的一系列亲电子试剂中的亲核加成。铂（II）催化剂和丙二烯底物经过加氢条件生成亲核烯丙基铂络合物，而无需使用化学计量的有毒和敏感的有机金属试剂。烯丙基铂中间体与CO和CN键反应以良好的产率产生相应的均烯丙基醇和胺衍生物。CN键的Pt催化的烯丙基化是在氢化条件下进行的第一个例子。在氘标记研究的基础上，提出了由PtH物种对烯丙基进行加氢金属化反应的反应机理。
• Dual Amine and Palladium Catalysis in Diastereo- and Enantioselective Allene Carbocyclization Reactions
  作者：Meiling Li、Swarup Datta、David M. Barber、Darren J. Dixon

  DOI：10.1021/ol303128s

  日期：2012.12.21

  A pyrrolidine and Pd catalyzed diastereoselective carbocyclization of aldehyde and ketone-linked allenes has been developed. The cooperative organo/metal-catalyzed cyclization reaction, which presumably proceeds via an enamine intermediate, is efficient and broad in scope. Also, it has been extended to a catalytic asymmetric variant using diarylprolinol-based organocatalysts to afford substituted cyclopentane and pyrrolidine reaction products in up to 82% ee.
• Enantioselective Arylative Cyclization of Allenyl Aldehydes with Arylboronic Acids under Pd(II)-diphosphine Catalysis
  作者：Hirokazu Tsukamoto、Tomotaka Matsumoto、Yoshinori Kondo

  DOI：10.1021/ol702966j

  日期：2008.3.1

  A Pd(OAc)(2)-SEGPHOS combination catalyzes the first enantioselective arylative cyclization of allenyl aldehydes with arylboronic acids to provide cis-fused five- and six-membered cyclic homoallylic alcohols. The excellent diastereo- and enantioselectivity and the fact that the reaction proceeds at room temperature in the absence of any additives make the process highly practical.
• Synthesis of<i>α</i>-Methylene-<i>γ</i>-butyrolactones: Ru-Catalyzed Cyclocarbonylation of Allenyl Aldehydes and Allenyl Ketones
  作者：Suk-Ku Kang、Kwang-Jin Kim、Young-Taek Hong

  DOI：10.1002/1521-3773(20020503)41:9<1584::aid-anie1584>3.0.co;2-y

  日期：2002.5.3