2026-10-13T13:54:33Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34036780 2026-09-30T20:05:48Z category_1 category_4 category_146 category_12 category_14 category_15 category_272 category_873 category_931 category_69 portal_63 item_type_6 month_year_09_2026

Palladium-Catalyzed Fast Decaging of Propargyloxycarbonyl (Proc)-Caged Guanidines Jing Zhang (23775) Lingling Xiang (12536290) Yunshi Liang (10863891) Yiting He (6397535) Yinjun Wang (515331) Shu Zhang (22238) Yunyao Li (18694575) Qin Tang (1896955) Song Chen (69646) Hong Qiu (315791) Biophysics Biochemistry Space Science Cell Biology Molecular Biology Neuroscience Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Information Systems not elsewhere classified Inorganic Chemistry mechanistic studies reveal liganded ” manner adjacent nitrogen atoms catalyzed fast decaging catalyzed decaging chemistry guanidino group accelerate decaging process caging group “ self triggered release previous allyloxycarbonyl phosphine ligand living cells high efficiency containing biomolecules analogous methods The Pd-catalyzed decaging reaction enables spatiotemporal control of amine-containing biomolecules, but analogous methods for guanidino-containing substrates remain underdeveloped. Here, we report a new Pd-catalyzed decaging chemistry for guanidines, with a propargyloxycarbonyl (Proc) moiety as the caging group in the absence of a phosphine ligand. Compared to our previous allyloxycarbonyl (Alloc)-based approach and the classical amine decaging chemistry, this system achieves remarkably accelerated decaging kinetics and high efficiency for both aromatic and aliphatic guanidines. Mechanistic studies reveal that the adjacent nitrogen atoms of the guanidino group accelerate the decaging process, probably in a “self-liganded” manner. Further application of this strategy is highlighted by the Pd-triggered release of Proc-caged guanidinyl fluorophores within minutes in living cells. 2026-09-30T00:00:00Z Text Journal contribution 10.1021/acs.joc.6c01127.s001 https://figshare.com/articles/journal_contribution/Palladium-Catalyzed_Fast_Decaging_of_Propargyloxycarbonyl_Proc_-Caged_Guanidines/34036780 CC BY-NC 4.0