1-Phenyl-2,3-butadienyl tosylcarbamate | 131141-51-0

• 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: 1-Phenyl-2,3-butadienyl tosylcarbamate
• CAS: 131141-51-0
• 化学式: C₁₈H₁₇NO₄S
• 分子量: 343.403
• InChiKey: VLWZWSZYNQPMAC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  80.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-Phenyl-2,3-butadienyl tosylcarbamate 在 sodium hydroxide 、 偶氮二异丁腈 、 camphor-10-sulfonic acid 、 三苯基氢化锡 、 碘 、 silver carbonate 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 33.5h， 生成 (4R,5R)-2,2-dimethyl-4-phenyl-5-vinyl-1,3-dioxolane
  参考文献：
  名称：

  Total synthesis of (±)-9-deoxygoniopypyrone. Application of the iodocyclofunctionalization reaction of bold α-allenic alcohol derivatives

  摘要：

  合成（±）-9-去氧戈尼欧吡喃（1）从α-烯丙醇5的描述。使用I₂和Ag₂CO₃对5的N-对甲苯磺酰基衍生物进行碘环功能化，以高度顺式选择性和区域选择性的方式提供了乙烯碘同位二醇4。为了在分子中引入第三个立体异构中心，探索了两条途径。乙烯碘化物的还原去碘和衍生的乙酮酸酯14的顺式选择性环氧化使用mCPBA提供了环氧化物15和16的混合物（2:1），其中所需的threo对显性异构体占主导地位。另外，乙酮酸酯14的二羟基化（OsO₄，NMO）产生了二醇21和22的混合物（2:3），在初级醇的单硅基化（TBDMSCl）后分离。主要硅醚erythro对显性异构体24通过甲磺酰化（MsCl，Et₃N）和环氧化物形成（TBAF）转化为所需的环氧化物15，立体化学反应发生反转。次要threo对显性异构体23也转化为所需的环氧化物15（TBAF；ArSO₂Cl；NaOMe）。环氧化物开环作用于锂乙炔基，并且生成的炔烃27经羰基化（MeLi，ClCO₂Me）得到α，β-乙炔基酯28。在Lindlar催化剂上的半氢化，随后在酸性条件下去除保护基提供（±）-8-epigoniodiol 30。最后，将30转化为（±）-9-去氧戈尼欧吡喃1在碱性条件下进行（DBU）。关键词：（±）-9-去氧戈尼欧吡喃，α-烯丙醇，碘环功能化，顺式二醇。

  DOI：

  10.1139/v97-212
• 作为产物：
  描述：

  苯甲醛 生成 1-Phenyl-2,3-butadienyl tosylcarbamate
  参考文献：
  名称：

  A highly stereoselective conversion of α-allenic alcohols to 1,2-syn amino alcohol derivatives via iodocarbamation

  摘要：

  DOI：

  10.1016/s0040-4039(00)97592-0

文献信息

• Palladium(II)-Catalyzed Tandem Reaction of Intramolecular Aminopalladation of Allenyl <i>N</i>-Tosylcarbamates and Conjugate Addition
  作者：Guosheng Liu、Xiyan Lu

  DOI：10.1021/ol016727p

  日期：2001.11.1

  A divalent palladium-catalyzed tandem cyclization-coupling reaction of allenyl N-tosylcarbamates and acrolein was developed. The reaction gave aldehyde-functionalized 2-oxazolidinones in one step with high regioselectivity. A mechanism involving intramolecular aminopalladation of allene, followed by insertion of alkene and C-Pd bond protonolysis, is proposed. [reaction: see text]

  开发了二价钯催化的烯丙基N-甲苯磺酰基氨基甲酸酯和丙烯醛的串联环化偶联反应。反应在一步中以高区域选择性得到醛官能化的2-恶唑烷酮。提出了一种机制，该机制涉及烯丙基的分子内氨基palpalpalation，然后插入烯烃和C-Pd键质子分解。[反应：看文字]
• Palladium-Catalyzed Stereoselective Allylaminocyclization and 1,3-Butadien-2-ylaminocyclization of Allenyl Tosylcarbamates
  作者：Masanari Kimura、Shuji Tanaka、Yoshinao Tamaru

  DOI：10.1021/jo00117a031

  日期：1995.6

  Palladium [PdCl2(PhCN)(2) or Pd-2(dba)(3) . CHCl3 (dba = dibenzylideneacetone)], in the presence of a base (Et(3)N or K2CO3) in THF at room temperature, catalyzes an allylaminocyclization of 2,3-butadienyl tosylcarbamates 1 with allylic chlorides to selectively provide trans-4,5-disubstituted 2-oxazolidinones 2 in good yields. Under similar conditions, Pd(PPh(3))(4) catalyzes an N-allylation of 1 to give 3. A limited number of 3,4-pentadienyl tosylcarbamates 5 undergo the allylaminocyclization to provide tetrahydro-1,3-oxazin-2-ones 6. In the absence of an allylic chloride, Pd(PPh(3))(4) and PdCl2(PhCN)(2) catalyze a formal dimerization of 1 to provide C-4-triene-substituted 2-oxazolidinones 4 in moderate to good yields.
• Iodocyclization of the (tolylsulfonyl)- and (trichloroacetyl)carbamates of secondary .alpha.-allenic alcohols. Highly diastereoselective synthesis of syn-1,2-amino alcohols and trans-5-alkyl-1-oxo-2-oxazolidine-4-carboxylic acids
  作者：Richard W. Friesen、Aleksandra E. Kolaczewska

  DOI：10.1021/jo00016a016

  日期：1991.8

  The iodocyclization of tosyl- and (trichloroacetyl)carbamates 9 and 10, respectively, of secondary alpha-allenic alcohols is described. The cyclofunctionalization reactions are highly diastereoselective, providing trans-5-alkyl-4-(1-iodoethylene)-2-oxazolidinones 11 and 12 as the major diastereomers in ratios of 6.3:1 to > 99: < 1. The mechanism of cyclization involves the initial formation of diiodides resulting from the addition of I2 to the terminal olefin of the allene moiety, followed by a kinetically controlled intramolecular SN2' displacement of iodide. Hydrolysis and acetylation of the N-tosyloxazolidinones 11 provide syn-1,2-amino alcohol derivatives 15. Alternatively, ozonolysis of the vinyl iodides derived from the cyclization of the (trichloroacetyl)carbamates 12 provides a novel, efficient, and highly diastereoselective route to trans-5-alkyl-2-oxazolidinone-4-carboxylic acids 25 and esters 26.
• Total synthesis of (±)-9-deoxygoniopypyrone
  作者：Richard W. Friesen、Suzanne Bissada

  DOI：10.1016/s0040-4039(00)77261-3

  日期：1994.8

  The total synthesis of (+/-)-9-deoxygoniopypyrone (1) from the alpha-allenic alcohol 2 is described. The synthesis is accomplished in 10 steps with the relative configuration of the three contiguous asymmetric centers being established by the highly diastereoselective formation of the synvicinal diet 3 via the iodo-cyclofunctionalization reaction of the allenic carbamate 5 and the epoxidation of the olefinic acetonide 11.
• Pd2+-catalyzed oxidative aminocarbonylation of O-2,3-butadienyl and O-3,4-pentadienyl N-tosylcarbamates
  作者：Masanari Kimura、Naoto Saeki、Shigeru Uchida、Hiroto Harayama、Shuji Tanaka、Keigo Fugami、Yoshinao Tamaru

  DOI：10.1016/s0040-4039(00)60413-6

  日期：1993.11

  Pd2+-catalyzed aminocarbonylation of O-2,3-butadienyl 1 and O-3,4-pentadienyl carbamates 5 stereoselectively provides 4-(1-methoxycarbonylvinyl)-1,3-oxazolidin-2-ones 2 and 4-(1-methyoxycarbonylvinyl)-1,3-oxazin-2-ones 6, respectively, in high yields.