Asymmetric Synthesis of Diamine Derivatives via Sequential Palladium and Rhodium Catalysis

Abstract

The use of a bifunctional nitrogen nucleophile and an allyl carbonate starting material in successive enantioselective palladium- and diastereoselective rhodium-catalyzed reactions enables the rapid assembly of unique amino aziridine products. Further elaboration of these materials affords complex, stereodefined polyamine architectures, thus demonstrating the power of these combined methods for simplifying asymmetric C−N bond construction.

Development of New Methods in Organic Synthesis and Their Applications to the Synthesis of Biologically Interesting Natural Products

“…Despite its usefulness, the success of this type of reaction is limited. [46][47][48][49][50] Although no reaction occurred when 2-phenylcyclohexenyl acetate was used as the substrate, allylic amination of 2-phenylcyclohexenyl carbonate 48 with benzylamine proceeded smoothly in acetonitrile, affording the corresponding product 49a in 93% yield and 93% ee (Chart 15). Chart …”

“…51) Although this type of transformation using oxygen nucleophiles has been investigated in detail by Trost et al, [52][53][54] there are limited investigations using nitrogen nucleophiles. 47,50) This background led us to examine the asymmetric allylic amination of 2-methoxycarbonyl 2-cyclohexenyl carbonate 51 with benzylamine using our catalyst system (Chart 17). Chart …”

Catalytic asymmetric synthesis using P-chiral diaminophosphine oxide preligands: DIAPHOXs

“…Although this type of transformation using oxygen nucleophiles has been investigated in detail by Trost et al 154e156 there are limited applications of nitrogen nucleophiles. 103,106 This background led us to examine asymmetric allylic amination of a 2-methoxycarbonyl 2-cyclohexenyl alcohol derivative 65 with benzylamine using our catalyst system (Table 10). The effect of the ligand structure revealed that the introduction of electron- Trace d a Pd (5 mol %) catalyst and 10 mol % of (S,R P )-1a were used.…”

Synthesis and Reactivity of Unique Heterocyclic Structures en Route to Substituted Diamines

“…1 Our laboratories have recently reported that two catalytic processes, Pd π-allyl coupling and Rh-catalyzed alkene aziridination, may be used in sequence to generate a previously unknown class of strained heterobicyclic products. 2 While the potential to synthesize differentially-substituted 1,2- and 1,3- diamines 3,4,5,6 from these unique oxathiadiazinane derivatives was evident, little was known about the factors that govern their stability and reactivity. Herein, we detail new protocols to prepare highly substituted forms of these heterocycles, and highlight for the first time the unusual stability and utility of Troc-protected oxathiadiazinanes for 1,2-diamine synthesis (Figure 1).…”