As the most studied and widely used chiral ligands, chiral phosphoramidite ligands have been rapidly developed in recent decades due to their simple synthesis, easy modification, and the ability to achieve excellent results in multiple reactions.
Phosphoramidites belong to phosphite derived amides, is an important class of trivalent phosphine ligands. Phosphoramidites differ from other trivalent phosphine ligands in that the structure of phosphoramidites contains a P-N bond and two P-O bonds with a pair of lone pair electrons on the phosphorus atom, which also becomes a possible coordination site when they are coordinated with metals. Phosphoramidite ligands can be divided into phosphanylidene groups and amine groups, and four typical phosphanylidene backbone structures are listed below: specifically, binaphthylenediphenol (BINOL) backbone, octahydrobinaphthylenediphenol (H8-BINOL) backbone, biphenol (BIPOL) backbone, and TADDOL backbone, as detailed in below:
BINOL Backbone General Structure | ||||||
A1375407 |
A495505 |
A1006117 |
||||
A1005842 |
A1002597 |
A1188217 |
||||
A796324 |
A385864 |
A1006200 |
||||
BINOL Backbone General Structure | ||||||
A413238 |
A264873 |
A1220018 |
||||
A1220021 |
A1220038 |
A103673 |
||||
A1220035 |
A1220017 |
A1220036 |
||||
BIPOL Backbone | General Structure |
A1371112 |
||||
TADDOL Backbone General Structure | ||||||
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Phosphoramidite ligands can be involved in many different asymmetric catalyses and can achieve better reaction results. In the following, the application of phosphoramidite ligands in many different asymmetric catalyses will be briefly described in terms of different reaction types.
In 2017, Shockley, S. E. et al. reported that the asymmetric allylation reaction of trisubstituted allylic electrophilic reagents with MAC (masked acyl cyanide, the following compound 1) catalyzed by iridium-chiral phosphoramidite, which was able to construct all-carbon quaternary allylic stereocenters with high selectivity. The yield can be as high as 99%, and the ee value can be as high as 94%[1][2].
In 2019, Jian-Jun Feng, Martin Oestreich et al. reported a three-component asymmetric coupling reaction of 1,3-dienes, diboron reagents and acylsilanes catalyzed by copper-chiral phosphoramidites, which was able to synthesize tertiary α-silanols with high regioselectivity, diastereoselectivity and enantioselectivity (up to 99% ee and d.r. > 20:1)[3].
In 2021, Weiwei Zi et al. reported that the asymmetric (3+2) cycloaddition reaction of phenyl-substituted methylene vinyl cyclic carbonate (VMCC) and nitroethylene catalyzed by Pd-chiral phosphoramidite was able to selectively prepare cyclopentanone with up to three chiral centers[4].