131719-69-2Relevant academic research and scientific papers
Transition-Metal-Free Formylation of Allylzinc Reagents Leading to α-Quaternary Aldehydes
Haraguchi, Ryosuke,Kusakabe, Akinori,Mizutani, Nakaba,Fukuzawa, Shin-Ichi
, p. 1613 - 1616 (2018/03/23)
The first example of formylation of allylzinc reagents using S-phenyl thioformate is presented. The reaction proceeded under mild conditions without any transition-metal catalyst, forming quaternary carbon centers with reactive functionalities, such as formyl and vinyl groups. Moreover, Barbier-type formylation of an allylic bromide with a sterically demanding thioformate was achieved. As a preliminary result, asymmetric formylation was conducted using a menthol-derived chiral thioformate.
Enantioselective intramolecular aldehyde α-alkylation with simple olefins: Direct access to homo-ene products
Comito, Robert J.,Finelli, Fernanda G.,Macmillan, David W. C.
supporting information, p. 9358 - 9361 (2013/07/26)
A highly selective method for the synthesis of asymmetrically substituted carbocycles and heterocycles from unactivated aldehyde-olefin precursors has been achieved via enantioselective SOMO-catalysis. Addition of a catalytically generated enamine radical cation across a pendent olefin serves to establish a general asymmetric strategy toward the production of a wide range of formyl-substituted rings with alkene transposition. Conceptually, this novel mechanism allows direct access to "homo-ene"-type products.
Enantioselective synthesis of tertiary and quaternary stereogenic centers: Copper/phosphoramidite-catalyzed allylic alkylation with organolithium reagents
Fananas-Mastral, Martin,Perez, Manuel,Bos, Pieter H.,Rudolph, Alena,Harutyunyan, Syuzanna R.,Feringa, Ben L.
supporting information; scheme or table, p. 1922 - 1925 (2012/04/17)
An efficient and highly enantioselective copper-catalyzed allylic alkylation of disubstituted allyl halides with primary and secondary organolithium reagents using phosphoramidite ligands is reported. The use of trisubstituted allyl bromides allows, for the first time, the enantioselective synthesis of all-carbon quaternary stereogenic centers with these reactive organometallic reagents.
