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P-Chiral 1,7-diphosphanorbornenes: from asymmetric phospha-Diels-Alder reactions towards applications in asymmetric
A A Zagidullin1, E S Oshchepkova1, I V Chuchelkin2
1Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, Kazan, Russia. almaz_zagidullin@mail.ru.
Abstract:
A straightforward synthesis of P-chiral polycyclic phosphines by an asymmetric Diels-Alder reaction of 1-alkyl-1,2-diphospholes and (5R)-(l-menthyloxy)-2(5H)-furanone (MOxF) is presented. The [4 + 2] cycloaddition reaction of 1,2-diphospholes 1-3 with MOxF (4) proceeded with high diastereoselectivity (de up to 90%) resulting in the corresponding enantiopure anti-endo-1,7-diphosphanorbornenes 5a-7a. The absolute configuration of 5-7 was proved by a variety of 1D/2D NMR correlation methods. The use of the anti-endo-1,7-diphosphanorbornene 5a in the Pd-catalyzed asymmetric allylic alkylation of cinnamyl acetate 8 with cyclic β-ketoesters 9a,b provided up to 52% ee.
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