Formal nucleophilic pyrrolylmethylation via palladium-based auto-tandem catalysis: switchable regiodivergent synthesis and remote chirality transfer

被引:11
作者
Chen, Zhi [1 ]
Li, Yu-Fan [1 ]
Tan, Shun-Zhong [1 ]
Ouyang, Qin [2 ]
Chen, Zhi-Chao [1 ]
Du, Wei [1 ]
Chen, Ying-Chun [1 ,2 ]
机构
[1] Sichuan Univ, West China Sch Pharm, Sichuan Res Ctr Drug Precis Ind Technol, Educ Minist & Sichuan Prov,Key Lab Drug Targeting, Chengdu 610041, Peoples R China
[2] Third Mil Med Univ, Coll Pharm, Chongqing 400038, Peoples R China
关键词
CYCLOISOMERIZATION; ACTIVATION; 1,6-ENYNES; PYRROLE; RHODIUM;
D O I
10.1039/d2sc05210e
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Although nucleophilic benzylation-type reaction to introduce various aromatic systems into molecules has been widely explored, the related pyrrolylmethylation version remains to be disclosed. Reported herein is a palladium-catalysed multiple auto-tandem reaction between N-Ts propargylamines, allyl carbonates and aldimines in the presence of an acid, proceeding through sequential allylic amination, cycloisomerisation, vinylogous addition and aromatisation steps. A diversity of formal pyrrolylmethylated amine products were finally furnished efficiently. In addition, switchable regiodivergent 3-pyrrolylmethylation and 4-pyrrolylmethylation were realised by tuning catalytic conditions. Moreover, remote chirality transfer with readily available enantioenriched starting materials was well achieved with an achiral ligand, relying on diastereoselective generation of eta(2)-Pd(0) complexes between Pd(0) and chiral 1,3-diene intermediates in the key vinylogous addition step. A few control experiments were conducted to elucidate the palladium-involved tandem reaction and regiodivergent synthesis.
引用
收藏
页码:12433 / 12439
页数:7
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