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首页> 外文学位 >Selective palladium- and rhodium-catalyzed processes: I. Enantioselective synthesis of tetrahydroquinolines, II. The asymmetric hydroformylation reaction, III. Silystannylation-cyclization of diynes and alleneynes .
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Selective palladium- and rhodium-catalyzed processes: I. Enantioselective synthesis of tetrahydroquinolines, II. The asymmetric hydroformylation reaction, III. Silystannylation-cyclization of diynes and alleneynes .

机译：选择性钯和铑催化的方法：I.四氢喹啉的对映选择性合成，II。不对称加氢甲酰化反应，III。二炔和丙二烯的甲硅烷基化环化。

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Chapter 1. Sharpless asymmetric epoxidation (>90%e.e.) of a o-nitrocinnamyl alcohol led to an intermediate that was transformed into a 3-hydroxy-substituted tetrahydroquinoline. High-yielding Heck coupling of an o-nitroaryl iodide and α-acetamidoacrylate followed by a highly enantioselective rhodium-catalyzed asymmetric hydrogenation (>98%e.e.) gave a rapid and general entry into both R and S amino acids, which were further reacted to produce a 3-amino-substituted tetrahydroquinolines. Both the 3-hydroxy and 3-amino tetrahydroquinolines could serve as intermediates for the synthesis of biologically relevant cyclopropapyrroloindoles.; Chapter 2. The ability of DIOP derivatives to function as ligands in the rhodiumcatalyzed asymmetric hydroformylation reaction was investigated. Under mild reaction conditions (3–10 bars of H2/CO gas pressure, 30–60°C), the hydroformylation of styrene, 2-vinylnaphthalene, vinyl acetate and N-vinylphthalimide using [1,4-disubstituted DIOP] ligands derived from D-mannitol led to improved regioselectivities ( e.g. linear to branched aldehyde ratio of 15:85 for the hydroformylation of styrene using (RSSR)-1,4-dimethyl-DIOP), compared to DIOP (e.g. linear to branched aldehyde ratio of 38:62 for the hydroformylation of styrene under the same reaction conditions). Steric (varying substituents at C1 and C4) or electronic (electron-withdrawing or donating groups on the phosphorous aryl rings) tuning of the modified DIOP ligands had little influence on the regioselection, possibly due to the lack of flexibility imposed by the isopropylidene ring which contains the C 2-C3 bond.; Chapter 3. The first example of a (Z,Z)- bis-alkylidenecyclohexane was synthesized by palladium-catalyzed silylstannylation-cyclization of a cis-4,5-O-isopropylidene-1,7-octadiyne-4,5-diol. The steric bulk of the silyl and stannyl substituents created an axial chirality in the structure, and the molecule exists as two diastereoisomers that do not display any fluxional behavior at temperatures below 60°C. This provided the first definitive example of a (Z,Z)-1,4-silylstannyldiene in which the atropisomerism has been frozen at or above room temperature. Silylstannylation of alleneynes derived from succinimide gave a rapid entry into highly functionalized indolizidines. While attempts synthesize bicyclic β-lactams by this route have not yet succeeded, preparation of several potentially useful allylstannane intermediates from β-lactam substrates highlighted the remarkable functional group compatibility of the silylstannylation reaction.
机译：第1章。 o -硝基肉桂醇的无尖锐不对称环氧化反应（> 90％e.e。）导致中间体转化为3-羟基取代的四氢喹啉。 o -硝基芳基碘化物和α-乙酰氨基丙烯酸碘化物的高产率Heck偶联，然后是高对映体选择性的铑催化的不对称氢化（> 98％ee），使得 R都可以快速且普遍地进入和 S 氨基酸，它们进一步反应生成3-氨基取代的四氢喹啉。 3-羟基和3-氨基四氢喹啉都可以用作合成生物学上相关的环丙吡咯并吲哚的中间体。 第二章。研究了DIOP衍生物在铑催化的不对称加氢甲酰化反应中作为配体的能力。在温和的反应条件下（3-10巴的H 2 / CO气压，30-60°C），苯乙烯，2-乙烯基萘，乙酸乙烯酯和 N -乙烯基邻苯二甲酰亚胺可提高区域选择性（例如线性与支化醛比例为15:85的苯乙烯加氢甲酰化使用（ RSSR ）-1,4-二甲基-DIOP），与DIOP相比（在相同反应条件下，苯乙烯加氢甲酰化的例如线性与支化醛比率为38:62）。改性DIOP配体的立体（C 1 和C 4 上的取代基不同）或电子（磷芳基上的吸电子或供电子基团）调节对区域选择，可能是由于含有C 2 -C 3 键的异亚丙基环缺乏柔性所致。 第3章。（ Z，Z ）--亚烷基亚环己烷的第一个例子是通过钯催化的甲硅烷基锡烷基化环化反应合成的。斜体>顺式 -4,5- <斜体> O -异亚丙基-1,7-辛二炔-4,5-二醇。甲硅烷基和甲锡烷基取代基的空间位阻在结构中产生了轴向手性，并且该分子以两种非对映异构体的形式存在，它们在低于60°C的温度下没有任何流动性。这提供了（ Z，Z ）-1,4-甲硅烷基锡烷基二烯的第一个确定性实例，其中阻转异构现象已在室温或高于室温的条件下冻结。源自琥珀酰亚胺的烯丙炔的甲硅烷基锡烷基化作用迅速进入了高度官能化的吲哚并咪唑。尽管通过这种途径合成双环β-内酰胺的尝试尚未成功，但是从β-内酰胺底物制备几种潜在有用的烯丙基锡烷中间体的过程突出了甲硅烷基锡烷基化反应的显着官能团相容性。

著录项

  • 作者

    Gallou, Isabelle.;

  • 作者单位

    The Ohio State University.;

  • 授予单位 The Ohio State University.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2002
  • 页码 265 p.
  • 总页数 265
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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