期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 45, 页码 24116-24123出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202107253
关键词
diastereoselectivity; imines; photocatalysis; redox reactions; reduction
资金
- AstraZeneca
- Leverhulme Trust [RPG-2017-069]
- Honjo International Scholarship Foundation
- The Netherlands Organization for Scientific Research (NWO)
- SURF Cooperative
- EPSRC [EP/J013501/1] Funding Source: UKRI
This study describes a reagent-controlled stereodivergent carbocyclisation of aryl aldimine-derived, photocatalytically generated alpha-amino radicals possessing adjacent conjugated alkenes. The reaction can afford either bicyclic or tetracyclic products, with high selectivity and good-to-excellent yields. Computational analysis using DFT revealed the reaction pathway and mechanistic rationale behind this finely balanced yet readily controlled photocatalytic system.
A reagent-controlled stereodivergent carbocyclisation of aryl aldimine-derived, photocatalytically generated, alpha-amino radicals possessing adjacent conjugated alkenes, affording either bicyclic or tetracyclic products, is described. Under net reductive conditions using commercial Hantzsch ester, the alpha-amino radical species underwent a single stereoselective cyclisation to give trans-configured amino-indane structures in good yield, whereas using a substituted Hantzsch ester as a milder reductant afforded cis-fused tetracyclic tetrahydroquinoline frameworks, resulting from two consecutive radical cyclisations. Judicious choice of the reaction conditions allowed libraries of both single and dual cyclisation products to be synthesised with high selectivity, notable predictability, and good-to-excellent yields. Computational analysis employing DFT revealed the reaction pathway and mechanistic rationale behind this finely balanced yet readily controlled photocatalytic system.
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