Acceleration Effects of Phosphine Ligands on the Rhodium-Catalyzed Dehydrogenative Silylation and Germylation of Unactivated C(sp3)–H Bonds

Autor:	Hirotaka Takeshima, Haruka Morita, Masahito Murai, Yoichiro Kuninobu, Kazuhiko Takai
Rok vydání:	2015
Předmět:	Steric effects chemistry.chemical_compound Silylation Chemistry Ligand Organic Chemistry Enantioselective synthesis Reactivity (chemistry) Bite angle Photochemistry Medicinal chemistry Desymmetrization Phosphine
Zdroj:	The Journal of Organic Chemistry. 80:5407-5414
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.5b00920
Popis:	The current work describes the marked rate of acceleration caused by phosphine ligands on the rhodium-catalyzed dehydrogenative silylation and germylation of unactivated C(sp(3))-H bonds. The reactivity was affected by the steric and electronic nature of the phosphine ligands. The use of the bulky and electron-rich diphosphine ligand (R)-DTBM-SEGPHOS was highly effective to yield the dehydrogenative silylation products selectively in the presence of a hydrogen acceptor. An appropriate choice of C2-symmetric chiral diphosphine ligand enables the asymmetric dehydrogenative silylation via the enantioselective desymmetrization of the C(sp(3))-H bond. The unprecedented catalytic germylation of C(sp(3))-H bonds with dehydrogenation was also examined with the combination of the rhodium complex and a wide bite angle diphosphine ligand to provide the corresponding 2,3-dihydrobenzo[b]germoles in good yield.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::69a4a53ecae67d4d6ccdf6417fc82f7b https://doi.org/10.1021/acs.joc.5b00920 Zobrazit plný text záznamu