Convenient access to pyrrolidin-3-ylphosphonic acids and tetrahydro-2H-pyran-3-ylphosphonates with multiple contiguous stereocenters from nonracemic adducts of a Ni(II)-catalyzed Michael reaction

A new synthetic strategy toward nonracemic phosphoryl-substituted pyrrolidines and tetrahydropyranes with three and five contiguous stereocenters is presented. Readily available β-keto phosphonates react with conjugated nitroolefins in the presence of a chiral Ni(II) complex to give nitro keto phosp...

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Bibliographic Details
Published in:Beilstein journal of organic chemistry 2020, Vol.16 (1), p.2073-2079
Main Authors: Reznikov, Alexander N, Nikerov, Dmitry S, Sibiryakova, Anastasiya E, Rybakov, Victor B, Golovin, Evgeniy V, Klimochkin, Yuri N
Format: Article
Language:English
Subjects:
asymmetric catalysis
Chemistry
Full Research Paper
michael addition
phosphonates
pyrrolidines
tetrahydropyranes
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Summary:A new synthetic strategy toward nonracemic phosphoryl-substituted pyrrolidines and tetrahydropyranes with three and five contiguous stereocenters is presented. Readily available β-keto phosphonates react with conjugated nitroolefins in the presence of a chiral Ni(II) complex to give nitro keto phosphonates with two stereocenters with excellent enantioselectivity and moderate to high diastereoselectivity. These products were used for a reductive cyclization leading to pyrrolidin-3-ylphosphonic acid and for reactions with aldehydes yielding tetrahydropyranylphosphonates as individual stereoisomers. These nonracemic heterocycles containing phosphoryl moieties are useful for designing new pharmacologically active compounds.
ISSN:1860-5397
1860-5397
DOI:10.3762/bjoc.16.174