Palladium-Catalyzed Formal anti -Markovnikov Hydroamidation of 1,3-Dienes with Disilane via 1,4-Silylamidation/Protodesilylation
Abstract Hydroamidation of 1,3-dienes with carboxamides remains underdeveloped, particularly for anti-Markovnikov selectivity. We report a disilane-mediated silicon relay strategy in which palladium-catalyzed 1,4-silylamidation generates an allylsilane intermediate that undergoes protodesilylation to furnish the first formal anti-Markovnikov hydroamidation of 1,3-dienes. Suppression of protodesilylation selectively affords 1,4-silylamidation products. Experimental and computational studies clarify the origin of the divergent reaction outcomes.
Authors
- Nobuki Katayama (ORCID: https://orcid.org/0000-0003-4649-3747)
- Kazuhiko Semba (ORCID: https://orcid.org/0000-0001-7903-4091)
- Tetsuaki Fujihara (ORCID: https://orcid.org/0000-0002-6687-2528)
- Hiroki Yamaguchi (ORCID: https://orcid.org/0000-0002-3808-2879)
- Yasushi Obora (ORCID: https://orcid.org/0000-0003-3702-9969)
- Kazuki Tabaru (ORCID: https://orcid.org/0000-0001-5587-5670)
- Tsz-Chun Chan
Institutions
- Kansai University (JP)
Publication Details
- Journal
- Organic Letters
- Published
- 2026-09-25
- DOI
- https://doi.org/10.1021/acs.orglett.6c03575
- Primary Topic
- Organoboron and organosilicon chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00