Selective Palladium‐Catalyzed Hydroformylation of Alkynes to α,β‐Unsaturated Aldehydes

Abstract

Atom-efficient: A selective palladium catalyst system is used for the hydroformylation of alkynes (see picture). In this syngas reaction, various alkynes were smoothly transformed to synthetically interesting α,β-unsaturated aldehydes in good yields with high regio- and stereoselectivity.

Selective Palladium‐Catalyzed Aminocarbonylation of Olefins with Aromatic Amines and Nitroarenes

“…Zuschriften were well-tolerated, and smoothly transformed to the corresponding functionalized amides in good yields and high selectivities for the linear product ( Table 2, entries [12][13][14][15]. It is noteworthy that the corresponding formamides were not observed in any of these cases.…”

“…BINAP, Dppp, L2, and L4) showed low activity in the formation of the desired product ( Table 1, entries [5][6][7][8][9][10][11][12][13][14]. Hence, some of our own developed N-phenylpyrrole-based bisphosphine ligands [14] with different steric properties were tested ( Table 1, entries [15][16][17]. To our delight, L10 was identified as the most promising ligand and the reaction afforded the desired product 3 aa with moderate conversion, albeit with good selectivity.…”

Sequential Hydroformylation/Diels–Alder Processes: One‐Pot Synthesis of Polysubstituted Cyclohexenes, Cyclohexadienes, and Phthalates from Alkynes

“…Initially, we investigated the formation of 4 a by using a one‐pot hydroformylation/Diels–Alder process starting from 3‐hexyne ( 1 a ). This substrate was treated under the standard hydroformylation reaction conditions recently reported by our research group, which allow the direct conversion of alkynes into α,β‐unsaturated aldehydes 20a. The α,β‐unsaturated aldehyde was directly subjected to the multicomponent Diels–Alder reaction conditions (including one equivalent of methanesulfonamide ( 2 a ), N ‐methylmaleimide ( 3 a ), and 3 mol % p ‐TsOH).…”

Following palladium catalyzed methoxycarbonylation by hyperpolarized NMR spectroscopy: a parahydrogen based investigation

“…In addition, the alkoxycarbonylatyion of 1-alkynes finds a further role in the formation of unsaturated carboxylic acids that feature as building blocks in a range of situations. 3,4 Consequently, these developments illustrate just how critical early studies on the mechanism of the methoxycarbonylation of alkenes, 2,5 and more generally the palladium catalysed hydroformylation of alkenes 6,7 were for the development of an array of new clean technologies. 3 For a number of years, the parahydrogen (p-H 2 ) 8 induced polarization (PHIP) 9, 10 effect has been used to yield mechanistic insight into a range of catalytic hydrogenation and hydroformlyation reactions besides monitoring the formation of metal hydride based products.…”