%0 Journal Article
%A Solé, Daniel
%A Vallverdú, Lluís
%A Solans, Xavier
%A Font-Bardia, Mercè
%A Bonjoch, Josep
%D 2004
%T Synthesis and Reactivity of Four-Membered
Azapalladacycles Derived from
N,N-Dialkyl-2-iodoanilines: Insertion Reactions of
Carbenes into the Carbon−Palladium Bond
%U https://acs.figshare.com/articles/journal_contribution/Synthesis_and_Reactivity_of_Four_Membered_Azapalladacycles_Derived_from_i_N_i_i_N_i_Dialkyl_2_iodoanilines_Insertion_Reactions_of_Carbenes_into_the_Carbon_Palladium_Bond/3346708
%R 10.1021/om034270c.s001
%2 https://ndownloader.figshare.com/files/5185921
%K acyl palladium complexes
%K 4 c
%K palladium complexes 4 b
%K solution azapalladacycles 4
%K N 2 CHTMS
%K Pd
%K Solid state structures
%K reaction conditions 4 b
%K κ 2
%K NMe
%K N 2 CHCO 2 Et
%X Three new four-membered azapalladacycles derived from N,N-dialkyl-2-iodoanilines have
been synthesized: [Pd(κ2-C6H4NMe2-2)I(PPh3)] (4a), [Pd{κ2-C6H4N(Me)CH2Ph-2}I(PPh3)] (4b),
and [Pd{κ2-C6H4N(Me)Pr-2}I(PPh3)] (4c). On heating in solution azapalladacycles 4a and
4c undergo aryl−aryl interchange between the palladium atom and the phosphine ligand
to give the phosphanyl-amine palladium complexes [PdPhI(PNMe2)] (7a) and [PdPhI{PN(Me)Pr}] (7c), respectively. Azapalladacycles 4a−c react with dichlorocarbene to give acyl
palladium complexes [Pd{κ2-C(O)C6H4NMe2-2}I(PPh3)] (8a), [Pd{κ2-C(O)C6H4N(Me)CH2Ph-2}I(PPh3)] (8b), and [Pd{κ2-C(O)C6H4N(Me)Pr-2}I(PPh3)] (8c), respectively. Smooth insertion
of N2CHCO2Et into the carbon−palladium bond of azapalladacycles 4a−c results in the
formation of the single-insertion products [Pd{κ2-CH(CO2Et)C6H4NMe2-2}I(PPh3)] (9a), [Pd{κ2-CH(CO2Et)C6H4N(Me)CH2Ph-2}I(PPh3)] (9b), and [Pd{κ2-CH(CO2Et)C6H4N(Me)Pr-2}I(PPh3)] (9c), respectively. On the other hand, complexes 4a and 4c react with N2CHTMS
to give mainly the single-insertion products [Pd{κ2-CH(SiMe3)C6H4NMe2-2}I(PPh3)] (10a)
and [Pd{κ2-CH(SiMe3)C6H4N(Me)Pr-2}I(PPh3)] (10c), respectively, while under similar
reaction conditions 4b affords N-benzyl-N-methyl-2-[(Z)-2-(trimethylsilyl)vinyl]aniline (11b)
as a consequence of a double-insertion process. Solid state structures of palladium complexes
4b, 8b·EtOAc, 9a, 9b, and 9c·Et2O have been determined by X-ray analysis.
%I ACS Publications