Rhodium-Catalyzed Reactions of Propargylamines With CO/H2. Formation of Pyrroles and Butenolides

Abstract

Rhodium-catalysed reactions of (arylpropargy1)arnines with CO/H2 give P-arylpyrroles in good yields. Reactions of (alkylpropargy1)amines gave alkylpyrroles together with butenolides which are formed in an unusual reaction that probably involves double carbonylation, reduction of one carbonyl function and removal of the amine function by hydrogenolysis.The single-crystal X-ray structure of 5-methyl-N,3-diphenylpyrrole-2-carboxamid is recorded.

Three Approaches to Catalytic Aqueous Organometallic Chemistry Involving Water Soluble Ligands, Some Modified Cyclodextrins as Ligands, and Reactions in an Aluminophosphate Cavity

“…However we have observed reductive loss of oxygen in the rhodium catalysed reaction of propargylamines [7]. It was of note that the product was isolated as the free amine.…”

A study of the effects of subunit pre-orientation for diarylpyrrole esters; design of new aryl-heteroaryl fluorescent sensors

“…10 Rhodium and zirconium catalysed reaction of alkynes, amines and carbon monoxide have been reported as procedures to unsymmetrically substituted derivatives but these methods require high pressure CO conditions. 11,12 Our approach followed a literature methodology which exploited a reductive cyclisation of electron deficient g-nitroketones with formamidinesulfinic acid. 13 The starting point for our synthesis were the 1,3-diarylpropenones (chalcones) 2.…”

“…17 There are no close pyrrole analogues of 1a-c available on the Cambridge Structural Database (CSD) reported to date using a search for the central pyrrole core with two C 6 aromatic rings attached. However, an example VUGDEG, 11,18 5-methyl-N,3diphenylpyrrole-2-carboxamide has the general substitution pattern of three carbon atoms replacing three of the H atoms on a pyrrole ring system, while XETXID, 19 ethyl 3-methyl-5phenylpyrrole-2-carboxylate differs from 1a by replacing a phenyl with a methyl group. This study of 1a-c highlights that functional groups at remote positions in a molecular system can introduce subtle differences in both the molecular and crystal structures as manifested in bond length/angles differences and overall intermolecular hydrogen bonding.…”

N‐Silyl‐Tethered Radical Cyclizations: A New Synthesis of γ‐Amino Alcohols.

“…The resulting aqueous layer was extracted several times with CH 2 Cl 2 . The combined organic layers were dried over anhydrous Na 2 SO 4 , filtered and evaporated in vacuo to give 1.27 g of pure hept-2-yn-amine 8 as a yellow oil. To a stirred solution of the latter (1.27 g, 11.4 mmol, 1.0 equiv.)…”