An efficient asymmetric Mannich-type reaction between α-tetralone-derived β-keto esters/amides and 1,3,5-triaryl-1,3,5-triazinanes was realized catalyzed by chiral N,N'–dioxide-Ni(ii)/Mg(ii) complexes.

Juvenile xanthogranuloma is a benign histiocytic skin disorder encountered primarily in infancy and childhood. Approximately 0.4% of cases exhibit ocular manifestations, which can result in glaucoma and blindness. We present a case of a 7-month-old male with unilateral glaucoma associated with Juvenile xanthogranuloma, and emphasize the importance of an ocular screening in patients with Juvenile xanthogranuloma, especially those with periocular lesions.

Ah ighly enantioselective formal conjugate allyl addition of allylboronic acids to b,g-unsaturated a-ketoesters has been realized by employing ac hiral Ni II /N,N'-dioxide complex as the catalyst. This transformation proceeds by an allylboration/oxy-Cope rearrangement sequence,p roviding af acile and rapid route to g-allyl-a-ketoesters with moderate to good yields (65-92 %) and excellent ee values (90-99 %ee). The isolation of 1,2-allylboration products provided insight into the mechanism of the subsequent oxy-Cope rearrangement reaction:s ubstrate-induced chiral transfer and ac hiral Lewis acid accelerated process.Based on the experimental investigations and DFT calculations,arare boatlike transition-state model is proposed as the origin of high chirality transfer during the oxy-Cope rearrangement.

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