Remote Nucleophilic Allylation by Allylrhodium Chain Walking. Issue 51 (20th August 2018)

• Record Type: Journal Article
• Authors: Groves, Alistair; Martínez, Jose I.; Smith, Joshua J.; Lam, Hon Wai
• Is Part Of: Chemistry. Volume 24:Issue 51(2018)
• Page Start: 13432
• Page End: 13436
• Publication Date: 2018-08-20
• Subjects: allylation -- chain walking -- homogeneous catalysis -- isomerization -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201803574
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1, 3‐dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and with an imine to give Z ‐homoallylic alcohols and amines, respectively. Abstract : Allylrhodium species obtained from hydrorhodation of 1, 3‐dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and with an imine to give Z ‐homoallylic alcohols and amines, respectively.