Enantioselective Palladium(II)‐Catalyzed Oxidative Aminofluorination of Unactivated Alkenes with Et₄NF⋅3 HF as a Fluoride Source

Abstract

The first asymmetric PdII‐catalyzed aminofluorination of unactivated alkenes using chiral quinoline‐oxazolines (Quox) as ligands has been developed. This reaction provides easy access to a wide array of enantiomerically enriched β‐fluoropiperidines in good yields and with excellent enantioselectivity. Notably, Et4NF⋅3 HF as a readily accessible nucleophilic fluoride source was found to play an essential role in the enantioselective control, and CsOCF3 also acts a key additive to improve the excellent ee value of products.

C(sp3)–H 1,3-diamination of cumene derivatives catalyzed by a dirhodium(ii) catalyst

“…Product 2aa can be reduced by LiAlH 4 to give monobenzenesulfonyl 13. In a solution of NaH, 13 was further reacted with iodomethane to produce the corresponding amine dimethylation product 14, and then by treatment with magnesium in methanol, [48][49][50] 1,3-diamine product 15 was successfully obtained (Scheme 4).…”

Palladium-catalyzed enantioselective (2-naphthyl)methylation of azaarylmethyl amines

“…10 Furthermore, enantioenriched pyridyl amines have been gaining momentum as ligands in asymmetric catalysis. [11][12][13][14][15][16] The increased interest in enantioenriched α-azaarylmethyl amines has led to a variety of methods for their synthesis. Typical strategies to install the acyclic stereocenter at the benzylic position of azaaryl derivatives include diastereoselective additions of organometallics to Ellman's sulfinimine (Scheme 1a).…”