Abstract
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.
Highlights
Сhiral phosphonates [1,2] and phosphoryl-substituted heterocycles [2,3,4] have received significant attention in recent years due to their wide range of biological activity
These products were used for a reductive cyclization leading to pyrrolidin-3-ylphosphonic acid and for reactions with aldehydes yielding tetrahydropyranylphosphonates as individual stereoisomers
For the synthesis of nonracemic polysubstituted pyrrolidin-3ylphosphonic acids and tetrahydropyranylphosphonates, we assumed that the 4-nitro-2-oxophosphonates – the Michael adducts of β-keto phosphonates and nitroolefins – are suitable precursors, considering that the Ni(II)-catalyzed Michael addition was carried out enantioselectively, and diastereoselectively, such has been previously described [45]
Summary
Сhiral phosphonates [1,2] and phosphoryl-substituted heterocycles [2,3,4] have received significant attention in recent years due to their wide range of biological activity. These products were used for a reductive cyclization leading to pyrrolidin-3-ylphosphonic acid and for reactions with aldehydes yielding tetrahydropyranylphosphonates as individual stereoisomers. The present work reports on the synthesis of nonracemic phosphoryl-substituted pyrrolidines and tetrahydropyranes via Ni(II)-catalyzed asymmetric Michael addition of β-keto phosphonates to conjugated nitroolefins.
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