Preparation of a fluorous chiral BINAP and application to an asymmetric Heck reaction

Repetitive Application of a Fluorous Chiral BINAP–Ru Complex in the Asymmetric Hydrogenation of Olefins

“…[24] Interestingly, as also reported by Nakamura et al, the commonly practised reduction method with trichlorosilane did not work. [7,17] The overall yield for both transformations from triflate 3 to BINAP 1 was 59 %. Despite the lengthening of the synthesis by one reduction step, we favour the latter alternative synthesis because of the easier purification process and ease of handling.…”

“…Hence, we alternatively investigated the synthesis of perfluoro-modified BINAP 1 via BI-NAP oxide 4, similar to the route Nakamura chose for the synthesis of his perfluoro-modified BINAP (Scheme 2). [7,17] The purification of BINAP oxide 4 was significantly easier with the use of this strategy relative to that of the original procedure and gave rise to isolated 4 in 69 % yield. The reduction was carried out by following the procedure of Imamoto in good yield by using trifluoromethanesulfonic acid methyl ester and LiAlH 4 .…”

“…[15] Amongst the variety of examples for modified BI-NAP were reports of BINAP ligands bearing perfluoroalkyl tails, which allowed their employment in FBS as well as their use in supercritical carbon dioxide as a reaction medium. [7,[16][17][18] However, to the best of our knowledge, there exists no example for the successful recovery and reuse of a perfluorinated BINAP-metal complex. Hope et al [18] have reported the application of a lightly perfluorinated BINAP in the ruthenium-catalysed asymmetric hydrogenation of ketones, where an attempt was made to recover the catalytic entity by filtration through FSG.…”

Separation of BINAPO enantiomers on brush-type chiral stationary phases

“…Prompted by continuous reporting on new applications of chiral bidentate ligands, and by our interest in developing new brush-type chiral stationary phases (CSPs) for specific applications, [7][8][9][10][11] we focused on the design and testing of a specific group of CSPs in order to perform chromatographic separation of BINAPO (1) enantiomers. So far in the literature the chromatographic enantioseparation of BINAPO 12 or its fluoro derivatives 13 is noted only for the purpose of the enantiomeric purity determination. There is a confusing use of acronym BINAPO in the literature.…”

Tris(perfluoroalkyl)silyl Entities as Unexpectedly Potent Tags for the Noncovalent Immobilization of Catalysts by Fluorous–Fluorous Interactions: Application to the Synthesis of Several Perfluoro‐Tagged Ligands

“…The synthesis of the (S)-binap ligand 28 (Scheme 5) equipped with (C 8 F 17 CH 2 CH 2 ) 3 Si tags was carried out with some modifications by the route reported by Nakamura and co-workers for the introduction of (C 6 F 13 CH 2 CH 2 ) 3 Si tags [35] [36]. They had applied their ligand for reactions in fluorous-biphasic systems.…”