Total synthesis of mycestericin A

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

“…Of note, in the above two examples, the inorganic base was used to avoid decomposition of the imidates by neutralizing acidic byproducts generated under the thermal conditions . Other syntheses based on Overman rearrangement accomplished by the Chida group as a key step include the syntheses of (+)-myriocin (single Overman rearrangement), mycestericin A (single Overman rearrangement), , A-315675 (double Overman rearrangement), and broussonetine F (orthoamide Overman rearrangement) . The Kim group completed the asymmetric total syntheses of (−)-antofine and (−)-cryptopleurine by applying an Overman rearrangement of an acyclic allylic alcohol as a key step to stereoselectively install a C–N bond …”

Recent advances in the total synthesis of polyhydroxylated alkaloids via chiral oxazines

“…In summary, our synthetic strategy utilizing syn , syn -, syn , anti -, anti , syn -oxazines as chiral building blocks enabled the synthesis of 30 diverse polyhydroxylated alkaloids, providing enantiomerically and diastereomerically pure products in a facile, efficient, and versatile manner. Various flexible strategies employed by other researchers, utilizing such as Overman rearrangement reaction, 38–42 tandem [4 + 2]/[3 + 2] nitroalkene cycloaddition, 45–49 Birch reduction, 50–54 and metal-mediated cross-coupling, 81–83 or with the use of key starting materials like chlorosulfonyl isocyanate, 61–67 Garner's aldehyde, 71–80 protected amino aldehydes, 84,85 and sugar-derived cyclic nitrone, 55–60,86–91 have been valuable. However, our strategy stands out due to its versatility, successfully synthesizing a range of natural products and offering potential applications in other natural products and pharmaceuticals like lycoricidine and miglitol.…”

“…Sphingofungins 38–41,126 isolated from fungi, are of significant interest owing to their biological activities as immunosuppressants and potential antifungal agents via the inhibition of serine palmitoyl-CoA transferase (SPT). In addition to sphingofungins, congeners such as myriocin ( M1 , Fig.…”

“…For instance, in alphabetical order, Chida and colleagues demonstrated the application of Overman rearrangement reactions involving allylic trichloroacetimidates to yield functionalized substructures of sphingolipids. Their work resulted in the total synthesis of various compounds, including myriocin, 38 sphingofungin E, 38 a ,39 sphingofungin F, 40 mycestericin A, 41 and broussonetine F. 42 They also reported the total synthesis of lycoricidine 43 and nojirimycin. 44…”