A recyclable CO surrogate in regioselective alkoxycarbonylation of alkenes: indirect use of carbon dioxide

Abstract

Herein, we report a Pd-catalysed alkoxycarbonylation of alkenes based on the use of a recyclable CO2 reduction product, the crystalline and air-stable N-formylsaccharin, as a CO surrogate. The carbonylation proceeds under ambient conditions in an exceptionally complementary regioselective fashion yielding the desired branched products from styrene derivatives and valuable linear esters from alkyl-substituted alkenes.

Metal‐Catalyzed Synthesis and Use of Thioesters: Recent Developments

“…Carbon monoxide was released from the CO‐surrogate N ‐formylsaccharin ( 12 , NFS) and the reaction was performed in a two‐chamber pressure tubes developed by Skrydstrup . This concept was previously reported for the alkoxycarbonylation of olefins …”

“…[19] This concept was previously reported for the alkoxycarbonylation of olefins. [20] Furthermore, af ew publications are available on the thiocarbonylation of alkynes. In 1997, Ogawa et al described the platinum-catalyzed carbonylative addition of thiols to terminal alkynes 13,g enerating a,b-unsaturated thioesters 14.…”

Pd/C in Propylene Carbonate: A Sustainable Catalyst–Solvent System for the Carbonylative Suzuki–Miyaura Cross‐Coupling Using N‐Formylsaccharin as a CO Surrogate

“…Arylboronic acid bearing a meta-methoxy group was coupled to give ketone 5h with conversion/selectivity of 79/70 % (Table 2, Entry 7). The fluorine-containing biaryl ketones 5n, 5o and 5p and the unsymmetrical ketones 5q, 5r and 5s bearing a combination of electron-donating and electron-withdrawing substituents were synthesized with high conversions and selectivities ranging from 50 to 73 % ( Table 2, Entries [13][14][15][16][17][18]. Ketone 5k containing an ester functionality could be synthesized from the corresponding arylboronic acid in 93 % conversion and 74 % selectivity (Table 2, Entry 10).…”

“…[13] Fleischer and co-workers reported the palladium-catalyzed alkoxycarbonylation of alkenes for the synthesis of aliphatic esters with N-formylsaccharin. [14] To the best of our knowledge, the carbonylative Suzuki-Miyaura cross-coupling using CO surrogates has only been performed under homogeneous catalytic protocols. Even though aryl bromides could be used as inexpensive coupling partners, the reaction protocols suffer from the use of toxic metal (molybdenum) carbonyl compounds as the CO surrogate, the requirement of a specialized two-chamber system and the use of phosphine ligands, toxic anhydrides and excess hydroxide base.…”

“…Moreover, the carbonylative Suzuki-Miyaura cross-coupling under CO surrogacy has been performed mostly in hydrocarbon solvents [5,6,[8][9][10] (anisole and toluene) and N,N-dimethylformamide. [14] Although the carbonylative crosscoupling could be effectively achieved and N-formylsaccharin underwent ready decarbonylation, the aforementioned amide, chlorinated and hydrocarbon solvents are considered toxic and unsustainable. [14] Although the carbonylative crosscoupling could be effectively achieved and N-formylsaccharin underwent ready decarbonylation, the aforementioned amide, chlorinated and hydrocarbon solvents are considered toxic and unsustainable.…”