Designing and Accurately Developing a [6 + 2] Dipolar Cycloaddition for the Synthesis of Benzodiazocines

Design and Application of Chiral Bifunctional 4-Pyrrolidinopyridines: Powerful Catalysts for Asymmetric Cycloaddition of Allylic N-Ylide

“…The ninhydrin-derived MBH carbonate 4 is also suitable for the (3 + 2) cycloaddition, providing product 5 with uncompromised results (>20:1 dr, 95.5:4.5 er) under identical conditions (Scheme a). C17 also promotes the (4 + 2) cycloaddition of a 2-aminobenzaldehyde-derived MBH carbonate recently developed by the Huang group (Scheme b) . In this reaction, achieving remote stereocontrol is assumed to be difficult.…”

“…C17 also promotes the (4 + 2) cycloaddition of a 2-aminobenzaldehydederived MBH carbonate recently developed by the Huang group (Scheme 2b). 15 In this reaction, achieving remote stereocontrol is assumed to be difficult. An excellent enantioselectivity was achieved in the allylic alkylation reaction of azlactone 9 by using C17 (Scheme 2c).…”

Cooperative photoactivation/Lewis base catalyzed [4 + 2] annulations of α-diazoketones andortho-amino MBH carbonates to access dihydroquinolinone frameworks

“…Moreover, designing a new type of MBH carbonate is another solution to overcome the limitation of the reaction sites. Recently, the Huang group disclosed a new type of MBH carbonate 14 by introducing a nucleophilic site based on the original structure in the ortho position of benzene, further expanding the MBH carbonate synthetic versatility as C4 or C6 synthons to realize [4 + 2] 14 a,b and [6 + 2] 14 c annulations with isocyanate affording 3,4-dihydroquinazolinone and benzodiazocine structures under mild conditions. However, the application of this new synthon in cooperative catalysis is under development, and could provide opportunities for synthesizing diverse pharmacophore architectures (Scheme 1B).…”

Synthesis of γ-hydroxy-γ-perfluoroalkyl butenolides and exocyclic double bond butanolides via regioselective allylic alkylations of MBH carbonates with 2-perfluoroalkyl-oxazol-5(2H)-ones

“…On the other hand, nucleophiles can directly attack the α-carbon position of MBH carbonates via an addition-elimination process to achieve α-allylic alkylation with a Brønsted base catalyst. 18 Therefore, we expect to synthesize γ-hydroxy-γ-perfluoroalkyl butenolides and γ-hydroxy-γ-perfluoroalkyl exocyclic double bond butanolides through the regioselective strategy of MBH carbonates.…”