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β‐Oxo phosphonates have been proven to be alternative Michael donors in Michael addition reactions to nitro olefins in the presence of cinchonine‐based bifunctional thiourea, affording a direct and atom‐economic approach to the efficient construction of synthetically and biologically valuable chiral acyclic α‐substituted β‐oxo phosphonates with high levels of enantioselectivity (up to 98 % ee).
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