Enantioselective Amination of β‐Keto Esters Catalyzed by Chiral Calcium Phosphates. Issue 37 (23rd May 2022)

• Record Type: Journal Article
• Authors: Wu, Zhenwei; Krishnamurthy, Suvratha; Satyanarayana Tummalapalli, K. S.; Xu, Jun; Yue, Caizhen; Antilla, Jon C.
• Is Part Of: Chemistry. Volume 28:Issue 37(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-23
• Subjects: catalyst reused -- catalyst recovered -- chiral calcium phosphates -- enantioselective amination -- β-keto esters; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202200907
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A catalytic enantioselective amination of β ‐keto esters using ( S )‐BINOL chiral calcium phosphate has been developed. The reaction produces chiral α ‐amino‐ β ‐keto ester derivatives in most cases with moderate to excellent enantioselectivities (up to 99 %) and good yields (up to 99 %). This mild synthetic method highlights a low catalyst loading and high catalytic efficiency. When the substrate backbone was changed to 1‐tetralone‐derived β ‐keto esters, unexpectedly high yields of selective redox products were obtained. The practicality of the reaction was realized by a scale‐up without any significant loss in the enantioselectivity and yield. Chiral calcium phosphate was successfully recovered and reused for four runs, indicating its stability and high catalytic activity. Abstract : Chiral 2‐aminoindane derivatives are a relatively common structural motif found in natural products and pharmaceutical molecules. Hence its highly desirable to develop efficient synthetic methods for enantioselective amination of β ‐keto esters. A non‐toxic chiral calcium phosphate‐catalyzed enantioselective amination of β ‐ketoesters with dibenzyl azodicarboxylate has been developed, generating chiral α ‐amino‐ β ‐ketoester derivatives in good yields and moderate to excellent enantioselectivities under mild conditions.