Fustero Santos, Miró Javier, Sánchez-Roselló María, del Pozo Carlos
Departamento de Química Orgánica, Universidad de Valencia, 46100-Burjassot (Spain); Laboratorio de Moléculas Orgánicas, Centro de Investigación Principe Felipe, 46012-Valencia (Spain).
Chemistry. 2014 Oct 20;20(43):14126-31. doi: 10.1002/chem.201403340. Epub 2014 Sep 5.
The dual ability of gold salts to act as π- and σ Lewis acids has been exploited in a tandem self-relay catalysis. Thus, triphenylphosphanegold(I) triflate mediated the intramolecular carbonyl addition of the amide functionality of homoprogargyl amides to a triple bond. The formation of a σ complex of the gold salt with the intermediate oxazine promoted a nucleophilic addition followed by a Petasis-Ferrier rearrangement. This tandem protocol, catalyzed by the same gold salt under the same reaction conditions, gave rise to the efficient synthesis of 2,3-dihydropyridin-4-(1 H)-ones, which contain a cyclic quaternary α-amino acid unit. The asymmetric version was performed by generating the starting materials from the corresponding sulfinylimines.
金盐作为π-和σ-路易斯酸的双重能力已被用于串联自中继催化。因此，三氟甲磺酸三苯基膦金（I）介导了高炔丙基酰胺的酰胺官能团与三键的分子内羰基加成反应。金盐与中间体恶嗪形成的σ-配合物促进了亲核加成，随后发生佩塔西斯-费里尔重排反应。在相同反应条件下，由同一金盐催化的这一串联反应方案能够高效合成含有环状季α-氨基酸单元的2,3-二氢吡啶-4-(1H)-酮。不对称反应版本是通过由相应的亚磺酰亚胺生成起始原料来进行的。
