000 02451 am a22002893u 4500
042 _adc
100 1 0 _aChen, Xiaofei
_eauthor
_91481
700 1 0 _aGilissen, Pieter J.
_eauthor
_91482
700 1 0 _aTinnemans, Paul
_eauthor
_91483
700 1 0 _aVanthuyne, Nicolas
_eauthor
_91484
700 1 0 _aRutjes, Floris P. J. T.
_eauthor
_91485
700 1 0 _aFeringa, Ben L.
_eauthor
_91486
700 1 0 _aElemans, Johannes A.A.W.
_eauthor
_91487
700 1 0 _aNolte, Roeland J.M.
_eauthor
_91488
245 0 0 _aEnantiodivergent epoxidation of alkenes with a photoswitchable phosphate manganese-salen complex
260 _c2022-09-22.
500 _a/pmc/articles/PMC7613796/
500 _a/pubmed/36353682
520 _aThe development of enantiodivergent catalysts capable of preparing both enantiomeric products from one substrate in a controlled fashion is challenging. Introducing a switching function into the catalyst can address this challenge, allowing the chiral reaction environment to reversibly change during catalysis. Here we report a photoswitchable phosphate ligand, derived from 2,2'-biphenol, which axially coordinates as the counter ion to an achiral manganese(III) salen catalyst, providing the latter with the ability to switch stereoselectivity in the epoxidation of alkenes. The enantiomers of the chiral ligand exist as a pair of pseudo-enantiomers, which can be interconverted by irradiation with light of different wavelengths. The opposite axial chirality of these pseudo-enantiomers is efficiently transferred to the manganese(III) salen catalyst. With this switchable supramolecular catalyst, the enantioselectivity of the epoxidation of a variety of alkenes can be controlled, resulting in opposite enantiomeric excesses of the epoxide products. This transfer of chirality from a photoswitchable anionic ligand to a metal complex broadens the scope of supramolecular catalysts.
540 _a
540 _ahttps://www.springernature.com/gp/open-research/policies/accepted-manuscript-termsUsers may view, print, copy, and download text and data-mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use: https://www.springernature.com/gp/open-research/policies/accepted-manuscript-terms
546 _aen
690 _aArticle
655 7 _aText
_2local
786 0 _nNat Synth
856 4 1 _uhttp://dx.doi.org/10.1038/s44160-022-00157-7
_zConnect to this object online.
999 _c1698
_d1698