The asymmetric total synthesis of (+)-subincanadine F has been achieved in only 9 steps from commercial tryptamine. A key step involves an Organo-SOMO-catalyzed α-arylation of aldehydes to construct the azepino[4,5-b]indole core. Finally, a subsequent intramolecular aza-Michael addition process leads to the formation of the 1-azabicyclo[4.3.1]decane framework. In addition, this Organo-SOMO catalytic strategy features a broad substrate scope, with diverse functionalized products afforded in generally moderate to good yields and good to excellent enantioselectivities.
Axially chiral allenes are valuable motifs in natural products and chiral ligands in asymmetric catalysis, yet methods to access enantioenriched difluoromethylated analogues remain undeveloped. Here we report the efficient copper-catalyzed SN2'-type substitution of propargylic alcohol derivatives with Zn(CF2H)2(DMPU)2, to deliver enantioenriched difluoromethylated allenes under mild conditions. This transformation proceeds with high regioselectivity, a broad substrate scope, and operational simplicity, providing a general strategy to construct CF2H-substituted chiral allenes of potential relevance to drug discovery.
An efficient cascade nitration-annulation-rearrangement of indole-tethered 1,6-enynes, tert-butyl nitrite (TBN) with O2 was developed for the synthesis of various NO2-dicarbonyl substituted pyrrolo[1,2-a]indole derivatives. This radical cascade process selected O2 as the carbonyl oxygen source and low-cost TBN as the nitro reagent. Meanwhile, the stable indole skeleton could smoothly undergo rearrangement to access dicarbonyl fused cycles. In addition, complex molecular transformation and scaled-up experiments examined the application of this tandem system. Finally, diverse mechanistic studies (including isotopic labeling, radical inhibition/capturation experiments) explored the reaction pathway.
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