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Iphosphino-l,l'-binaphthyl (MAP) was used as the ligand instead of BINAP, the reaction was complete at 60 °C in 5 min, suggesting that aminophosphines may become the ligands of choice for the Hartwig-Buchwald coupling
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Interestingly, when 2-amino-2'-diphenyIphosphino-l,l'-binaphthyl (MAP) was used as the ligand instead of BINAP, the reaction was complete at 60 °C in 5 min, suggesting that aminophosphines may become the ligands of choice for the Hartwig-Buchwald coupling. For the preparation of MAP, see the adjacent paper.
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For the Preparation of MAP, See the Adjacent Paper.
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5d No loss of enantiomeric purity was observed for (R)-16 by chiral HPLC.
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2Zn and PhCHO in the presence of (S)-(-)-2,2-dimethyl-5,5-diphenyl-4-isopropyl-1,3-oxazolidine, which apparently involves zinc amide as the reactive species lacking chelation:
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2-Zn to aldehydes, thus breaking the hegemony of amino alcohol ligands in this area. The mechanism is believed to involve transmetalat.ion so that the ethyl is first transferred from the zinc atom to the titanium chelated by the diol ligand. Presumably, the latter chiral species then reacts with the aldehyde: (a) Mon, M.; Nakai, T. Tetrahedron Lett. 1997, 38, 6233. Even more recently, functionalized polyBINOLs have been demonstrated to be capable of catalyzing the same reaction without the need of an additive:
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28b,c
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-
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119
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33744876295
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note
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41b (note that a similar effect is known in cuprate chemistry). The latter approach is awaiting its chiral version, thereby opening an exciting new avenue to our NOBIN-derived ligands.
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