Chiral Sulfoximine Mediated Cobalt-Catalyzed Atropselective C-H Annulation of Ynamides.

An achiral Cp*Co(III)-catalyzed enantioselective C-H activation/annulation of chiral sulfoximine-enabled thioamides with ynamides is presented herein. This method successfully synthesizes axially chiral five-membered 2-amidoindenones with good enantiocontrol. Interestingly, the annulation with chiral oxazolidone-containing ynamides could provide a separable mixture of diastereomers (up to ~10 : 1 dr). Moreover, enantiopure sulfoximines could be recovered with ~99 % purity, making this method practical. DFT studies show valuable insight into the mechanism and origin of asymmetric induction.

Gold(I)-catalysed cyclisation of (E)-ketene-N,O-acetals: a synthetic route toward spiro-oxazole-γ-lactones.

In this study, we developed a cascade 5,5-cyclisation of internal ketene-N,O-acetals utilizing homogeneous Au(I) catalysis. This process involves an initial 5-exo-dig carbocyclisation, followed by a 5-exo-dig heterocyclisation that stereoselectively incorporates the O-atom of a water molecule into an N-tethered propargyl alkyne. This sequential reaction results in the formation of one C-C, two C-O, and two C-I bonds, ultimately leading to the synthesis of spiro-α-iodo-γ-lactone structures featuring oxazole rings in good yields.

Asymmetric Total Synthesis of the Putative Structure of Diplopyrone.

The first asymmetric total synthesis of the putative structure of diplopyrone was achieved in 17 linear steps starting from cis-1,4-butene-diol. The synthetic route features iodine-catalyzed tandem isomerization followed by C-O and C-C bond formation reaction strategy developed by our own group to construct the trans-2,6-disubstituted dihydropyran ring, asymmetric α-aminoxylation reaction, and Still-Gennari (Z)-selective olefination reactions. Careful comparison of 1H and 13C NMR spectroscopic data as well as investigation of the UV and circular dichroism spectrum in trifluoroethanol for compound 2 suggest that the putative structure for diplopyrone {6-[(1S)-1-hydroxyethyl]-2,4a(S),6(R),8a(S)-tetrahydropyran[3,2-b]pyran-2-one} requires revision.

A 6-endo-dig Thiolative Cyclization of Yne-Ynamides: Access to Thiodihydropyridin-2-ones.

A straightforward regioselective intramolecular 6-endo-dig cyclization of yne-tethered ynamide is herein developed. The reaction involves an intramolecular enolate attack of ketene-N,O-acetals, generated in situ from yne-ynamide and methanesulfonic acid, to the alkyne moiety activated by a sulfonium cation. The transformation enables access to structurally diverse 5-(arylthio)-3,6-dihydropyridin-2(3H)-ones with broad functional group compatibility. The recovery of S-protecting groups and synthetic applications of the products make the transformation useful.

Total Synthesis and Stereochemical Revision of 4,8-Dihydroxy-3,4-dihydrovernoniyne.

The first asymmetric total synthesis of two possible diastereomers (4S,5R)-4,8-dihydroxy-3,4-dihydrovernoniyne 5 and (4S,5S)-4,8-dihydroxy-3,4-dihydrovernoniyne 5a is accomplished. Salient features of the synthesis involve Cadiot-Chodkiewicz coupling and Sonogashira cross-coupling of terminal acetylenes. Detailed comparison of the 1H and 13C NMR data and specific rotation with that of the natural product led to the revision of the absolute stereochemistry of the natural product as (4S,5S)-4,8-dihydroxy-3,4-dihydrovernoniyne 5a.