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2.4.1.4 Kinetic Resolution of Secondary Alcohols Using Manganese–Salen Complexes

DOI: 10.1055/sos-SD-202-00074

Stoltz, B.; Ebner, D. C.; Park, N.Science of Synthesis: Stereoselective Synthesis, (20112228.

Manganesesalen complexes are widely used in asymmetric oxidations, typically in heteroatom-transfer reactions.[‌56‌] It is only recently, however, that they have been employed in the kinetic resolution of secondary alcohols. The first example of the enantioselective oxidation of secondary alcohols using a manganesesalen catalyst was reported in 1998 by Katsuki in the course of benzylic hydroxylation studies with manganesesalen catalyst 46 using iodosylbenzene as the bulk oxidant.[‌57‌] In this study, the R-isomer of 3,3-dimethylindan-1-ol is resolved with a kfast/kslow of 4.2 (Scheme 25).

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M8 M8 M8 M Meeeeeeeee eeeee/eeeee ee (%) ee Meeeeeeee 88 Meeeeeeeee (%) Mee
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Me Me e-Me MM8 Me8MMe (8eee%), MeM(MMe)8 (8.8 eeeee), M8M, ee, 8e 88 88 88e [‌88‌]
8-MeM8M8 Me e-Me Me MMe (8eee%), MeM(MMe)8 (8.8 eeeee), M8M/eeeeeee (8:8), ee, 8e >88 >88 88e [‌88‌]
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References