Catalytic Methods for Carbon-Carbon and Carbon-Heteroatom Bond Formation

描述（由申请人提供）：提出了几个由亲电性金配合物催化的新反应。主要重点放在对映选择性C-C和C-X键结构的发展。一般来说，这些反应包括激活？-键作为亲电试剂，在某些情况下，通过配位与阳离子金(I)配合物活化亲核试剂。一系列通过炔或烯活化的对映选择性转化过程将被研究。提议的研究包括手性磷金(I)配合物和/或手性阴离子催化的对映选择反应。这些反应包括通过炔引发的环级联反应或通过向烯烯加成碳亲核试剂形成的对映选择性C-C键。后者将应用于氟德罗类生物碱的合成。对映选择性的分子间加成亲核试剂，要么直接激活？-键或阳离子中间体，也被提出。将研究从炔中原位生成金(I)-类碳中间体的方法及其在对映选择性环加成反应中的应用。此外，金(I)催化的对映选择反应将通过活化炔烃作为亲核试剂进行研究。总的来说，提出的反应包括亲电和亲核活化，并提供对映选择性进入广泛的碳和杂环结构。还提出了金催化烯烃的反应。这些转化包括金催化的亲核试剂直接加成烯烃和金催化的烯烃氧化二官能化。前者研究手性金配合物或质子（醇）与手性金配合物配位产生的Bronsted酸催化的分子内和分子间对映选择性加成反应。此外，金催化烯烃的氧化功能化，由金诱导的亲核加成引发？-债券，将被开发。这类反应包括亲核试剂与烯烃分子内和分子间加成的转化，以及由此产生的金中间体与亲核试剂（如硼酸）的分子内和分子间反应。

DESCRIPTION (provided by applicant): Several new reactions, catalyzed by electrophilic gold complexes, are proposed. A major emphasis is placed on the development of enantioselective C-C and C-X bond constructions. In general, these reactions involve activation of ?-bonds as electrophiles, in some cases activation of nucleophiles, by coordination to cationic gold(I) complexes. A range of enantioselective transformation proceeding via alkyne or allene activation will be investigated. The proposed studies include enantioselective reactions catalyzed by chiral phosphinegold(I) complexes and/or chiral anions. These reactions include enantioselective C-C bond formation through alkyne initiated cyclization cascades or by addition of carbon nucleophiles to allenes. The latter will be applied to the synthesis of the flinderole alkaloids. Enantioselective intermolecular addition of nucleophiles, either directly to the activated ?-bond or to a cationic intermediate, is also proposed. Methods that involve in situ generation of gold(I)-carbenoid intermediates from alkynes and their use in enantioselective cycloaddition reactions will be examined. Additionally, gold(I)-catalyzed enantioselective reactions that proceed through activation of alkynes as nucleophiles will be investigated. Taken together, the proposed reactions encompass both electrophile and nucleophile activation and provide enantioselective entries into a wide range of carbo- and heterocyclic structures. Gold-catalyzed reactions of alkenes are also proposed. These transformations include gold-catalyzed direct addition of nucleophiles to alkenes and gold-catalyzed oxidative difunctionalization of alkenes. In the former, intra- and intermolecular enantioselective addition reactions catalyzed by chiral gold complexes or Bronsted acids generated by coordination of protic species (alcohols) to chiral gold-complexes will be examined. Additionally, gold-catalyzed oxidative functionalization of alkenes, initiated by gold-induced nucleophilic addition to the ?-bond, will be developed. This reaction class includes transformations involving intra- and intermolecular addition of nucleophiles to alkenes and intra- and intermolecular reaction of the resulting gold intermediate with nucleophiles (such as boronic acids).