| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1345248 | Tetrahedron: Asymmetry | 2014 | 7 Pages |
The PhthalaPhos ligands, chiral BINOL monophosphites endowed with a phthalamide group, have been screened in the synthesis of 1-vinyltetrahydroisoquinolines by intramolecular palladium-catalysed asymmetric allylic amidation (AAA) of achiral tosylamidocarbonates. Identification of the best ligand followed by optimisation of the reaction conditions allowed the desired product to be obtained with up to 83% ee. Remarkably, the reaction is stereoconvergent, affording the same enantiomer of the desired product regardless of the geometry of the allylic carbonate’s double bond, which allows, in principle, the use of E/Z mixtures.
Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide
N1-(3,5-Bis(trifluoromethyl)phenyl)-N2-(3-((11bS)-dinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepin-4-yloxy)phenyl)phthalamideC42H25F6N2O5P[α]D20 = +43.3 (c 0.96, acetone)Source of chirality: (S)-(−)-1,1′-Bi(2-naphthol) (BINOL)Absolute configuration: (S)
(R)-6,7-Dimethoxy-2-tosyl-1-vinyl-1,2,3,4-tetrahydroisoquinolineC20H23NO4See = 83% on Chiralpak AD-H HPLC column[α]D20 = −83.5 (c 0.185, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
