Directly accessing the alkyne-aldehyde-amine (A3) coupling catalytic cycle using molecular gold(I) acetylide complexes for synthesizing propargylamines and amino indolizines

被引:1
作者
Singh, Jyoti [1 ]
Dua, Purva [1 ]
Rajaraman, Gopalan [1 ]
Ghosh, Prasenjit [1 ]
机构
[1] Indian Inst Technol Bombay Powai, Dept Chem, Mumbai 400076, India
来源
MOLECULAR CATALYSIS | 2024年 / 565卷
关键词
Acyclic aminooxy carbene (AAOC); Gold(I); Acetylide; Alkyne; Amine; Aldehyde; A; 3; coupling; Propargylamine; Indolizine; DFT studies; Non-covalent Au; H-C interaction; N-HETEROCYCLIC CARBENE; TERMINAL ALKYNES; ALKYNYLATION/CYCLIZATION REACTION; MONOAMINE-OXIDASE; BASIS-SETS; PALLADIUM; CYCLOADDITION; DERIVATIVES; EFFICIENT; ENERGY;
D O I
10.1016/j.mcat.2024.114387
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The gold(I) acetylide complexes of Acyclic Aminooxy Carbene (AAOC) ligands, [{(4-R1-2,6-t-Bu2-C6H2O)(NCy2)} methylidene]Au[C---C(p-C6H4R2)] [where R1 = H; R2 = H (1), and R1 = t-Bu; R2 = H (4)] efficiently catalyzed the three-component Alkyne-Aldehyde-Amine (A3) coupling yielding propargylamine and amino indolizine compounds, thereby implicating its direct role in the catalytic cycle. The DFT studies performed on a simplified gold(I) precatalyst, [{(2,4,6-Me3-C6H2O)(NCy2)}methylidene]Au[C---CPh] (4'), at B3LYP-D3/def2-TZVP of theory implicated the role of non-covalent Au center dot center dot center dot H-C interactions in the A3 coupling reactions producing propargylamine and subsequently amino indolizine via intramolecular cyclization of propargylamine followed by an intramolecular 1,2-hydrogen transfer-step for the 2-formylpyridine substrate. The non-covalent Au center dot center dot center dot H-C (alkyl) and Au center dot center dot center dot H-C(aryl) interactions participate in tandem to influence the overall reaction kinetic barrier, and thereby illustrating the importance of such interactions in gold catalysis. The gold(I) acetylide complexes, [{(4-R1-2,6-t-Bu2-C6H2O)(NCy2)}methylidene]Au[C---C(p-C6H4R2)] [where R1 = H; R2 = H (1), Me (2), OPh (3): R1 = t-Bu; R2 = H (4), Me (5), OPh (6)] were conveniently synthesized from the corresponding chloro analogues [{(4-R1-2,6-t-Bu2-C6H2O)(NCy2)}methylidene]AuCl (where R1 = H, t-Bu) by the treatment with terminal alkyne HC---C(p-C6H4R2) (where R2 = H, Me, OPh) in the presence of K2CO3 as a base in ca. 88-95 % yield.
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页数:24
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