Gold(i)-catalyzed diastereoselective synthesis of 1-α-oxybenzyl-1: H -indenes
The gold(i)-catalyzed oxycyclization of β-aryl monosubstituted o-(alkynyl)styrenes gives rise to 1-α-methoxy or 1-α-hydroxybenzyl-1H-indenes in a diastereospecific way. In contrast to β,β-disubstituted o-(alkynyl)styrenes, the stereochemical outcome of this process, diastereospecific reaction supports the higher contribution of a gold intermediate with a cyclopropylcarbene-like character.
Virumbrales, Cintia,Suárez-Pantiga, Samuel,Solas, Marta,Fernández-Rodríguez, Manuel A.,Sanz, Roberto
Gold(i)-catalyzed nucleophilic cyclization of β-monosubstituted: O -(alkynyl)styrenes: A combined experimental and computational study
The stereospecific gold(i)-catalyzed nucleophilic cyclization of β-monosubstituted o-(alkynyl)styrenes to produce C-1 functionalized 1H-indenes including challenging substrates and nucleophiles, such as β-(cyclo)alkyl-substituted o-(alkynyl)styrenes and a variety of alcohols as well as selected electron-rich aromatics, is reported. DFT calculations support the stereochemical outcome of the process that involves the formation of a key cyclopropyl gold carbene intermediate through a regiospecific 5-endo cyclization.
Virumbrales, Cintia,Solas, Marta,Suárez-Pantiga, Samuel,Fernández-Rodríguez, Manuel A.,Marín-Luna, Marta,López, Carlos Silva,Sanz, Roberto
supporting information
p. 9924 - 9932
(2019/12/06)
Drawing from a pool of radicals for the design of selective enyne cyclizations
Despite the possibility of intermolecular attack at four different locations, the Bu3Sn-mediated radical cyclization of aromatic enynes is surprisingly selective. The observed reaction path originates from the least stable of the equilibrating pool of isomeric radicals produced by intermolecular Bu3Sn attack at the π-bonds of substrates. The radical pool components are kinetically self-sorted via 5-exo-trig closure, the fastest of the four possible cyclizations. The resulting Sn-substituted indenes are capable of further transformations in reactions with electrophiles.
Mondal, Sayantan,Mohamed, Rana K.,Manoharan, Mariappan,Phan, Hoa,Alabugin, Igor V.
supporting information
p. 5650 - 5653
(2013/12/04)
Regio- and stereoselective construction of highly functionalized 3-benzazepine skeletons through ring-opening cycloamination reactions catalyzed by Gold
Ring size under control: Highly functionalized 1-amino- or 1-hydroxy-1H-benzo[d]azepines have been prepared through a gold-catalyzed cyclization of (o-alkynyl)phenyl aziridines with heteronucleophiles. After removal of the phthalimido group, the products can be further transformed into 1H-benzo[d]azepin-1-ones (see scheme; IBX=2-iodoxybenzoic acid, Phth=pthalimido).
Du, Xiangwei,Yang, Shuang,Yang, Jingyu,Liu, Yuanhong
p. 4981 - 4985
(2011/06/17)
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