55373-76-7Relevant articles and documents
Halogen-Substituted Allenyl Ketones through Ring Opening of Nonstrained Cycloalkanols
Wu, Penglin,Ma, Shengming
supporting information, p. 2533 - 2537 (2021/04/13)
An efficient synthesis of halogen-substituted allenyl ketones via Ag-catalyzed oxidative ring opening of allenyl cyclic alcohols under mild reaction conditions has been achieved. The reaction features a wide substrate scope and excellent regioselectivity. The synthetic potential of the products has been demonstrated by their conversion to stereodefined alkenes and heterocyclic compounds.
Alkyne Linchpin Strategy for Drug:Pharmacophore Conjugation: Experimental and Computational Realization of a Meta-Selective Inverse Sonogashira Coupling
Bhowmick, Suman,Guin, Srimanta,Kumar Singh, Vikas,Maiti, Debabrata,Paton, Robert S.,Porey, Sandip,Zhang, Xinglong
supporting information, p. 3762 - 3774 (2020/03/10)
The late-stage functionalization (LSF) of pharmaceutical and agrochemical compounds by the site-selective activation of C-H bonds provides access to diverse structural analogs and expands synthetically-accessible chemical space. We report a C-H functionalization LSF strategy that hinges on the use of an alkyne linchpin to assemble conjugates of sp2-rich marketed pharmaceuticals and agrochemicals with sp3-rich 3D fragments and natural products. This is accomplished through a template-assisted inverse Sonogashira reaction that displays high levels of selectivity for the meta position. This protocol is also amenable to distal structural modifications of α-amino acids. The transformation of alkyne functionality to other functional groups further highlights the applicative potential. Computational and experimental mechanistic studies shed light on the detailed mechanism. Turnover-limiting 1,2-migratory insertion of the bromoalkyne coupling partner occurs after relatively fast C-H activation. While this insertion occurs unselectively, regioconvergence results from one of the adducts undergoing a 1,2-trialkylsilyl migration to form the alkynylated product. A heterobimetallic Pd-Ag transition structure is essential for product formation in the β-bromide elimination step.
Palladium(II)-Catalyzed Site-Selective C(sp3)?H Alkynylation of Oligopeptides: A Linchpin Approach for Oligopeptide–Drug Conjugation
Liu, Tao,Qiao, Jennifer X.,Poss, Michael A.,Yu, Jin-Quan
supporting information, p. 10924 - 10927 (2017/08/30)
The palladium(II)-catalyzed C(sp3)?H alkynylation of oligopeptides was developed with tetrabutylammonium acetate as a key additive. Through molecular design, the acetylene motif served as a linchpin to introduce a broad range of carbonyl-containing pharmacophores onto oligopeptides, thus providing a chemical tool for the synthesis and modification of novel oligopeptide–pharmacophore conjugates by C?H functionalization. Dipeptide conjugates with coprostanol and estradiol were synthesized by this method for potential application in targeted drug delivery to tumor cells with overexpressed nuclear hormone receptors.
