Allylic selenides in organic synthesis: new methods for the synthesis of allylic amines

N,N,N-Triphenylselenylisocyanuric Acid (TPSCA): A New Versatile Reagent for α-Phenylselenenylation of Aldehydes and Ketones

“…14d,20 We observed that the reaction of hexanal with TPSCA as the electrophilic selenium reagent occurred in the presence of 20 mol% L-proline in CH 2 Cl 2 at room temperature to afford the desired selenenylation product in 77% yield (Table 1, entry 1). Encouraged by this result, we explored four additional amines under the same reaction conditions (entries [2][3][4][5]. The results showed that L-prolinamide was the best catalyst of the five that were tested.…”

“…The L-prolinamide-promoted reaction was complete within 10 minutes and resulted in 85% yield of product (entry 2). We also observed that piperidine, piperazine, and pyrrolidine, which could be used in a procedure that requires preformation of an enamine, were not good catalysts for this process when 20 mol% loading was employed (entries [3][4][5]. The results suggest that the amide group in L-prolinamide or the carboxylic acid group in L-proline are essential for catalyst activity.…”

α-Arylchalcogenation of Aldehydes and Ketones with Diaryl Dichalcogenides Promoted by K3PO4

“…For example, α-phenylseleno aldehydes and ketones can be converted into the corresponding synthetically useful α,β-unsaturated carbonyl compounds through selenoxide elimination reactions [10][11][12]. In addition, these compounds can be transformed into other important organic intermediates such as amines [13], α-amino acids [14], allylic alcohols [15], aziridines [16], and α-hydroxy esters [17].…”

Theoretical Studies of [2,3]-Sigmatropic Rearrangements of Allylic Selenoxides and Selenimides

“…[2,3]-Sigmatropic rearrangements of allylic selenoxides and selenimides ( Figure 1 a) are important tools for the synthesis of primary, secondary and tertiary allylic alcohols and amines [ 1 ]. Examples of applications of interest to natural products and bioorganic chemistry include the conversion of A-type prostaglandin to J-type [ 2 ], the enantioselective total synthesis of the marine oxylipin solandelactone E [ 3 ], as well as in the synthesis of sterols [ 4 ] and non-natural amino acids [ 5 ]. [2,3]-Sigmatropic rearrangements of selenoxides have also been used for intrastrand cross-linking of DNA [ 6 ].…”