Computational Investigation of Multifaceted Cationic Rearrangement and Stereo- and Regioselectivity in the Formation of Dysideanone’s Analogues

Abstract

Mechanistic studies of regiodivergent arylations of cycloalkanols to furnish enantioenriched dysideanone's analogues are performed by employing density functional theory (DFT) calculations (B3LYP-D3(SMD)/6-311++G**//B3LYP-D3/6-31+G** level of theory). On the basis of our calculations, remote γ′-C−H arylation is preferred for unsubstituted carbinol 1, an outcome from combined factors like carbocationic stability, less steric hindrance during C−C coupling, and facile dearomatization. Meanwhile, in the presence of dimethyl substituent 1 Me , regioselective γ-arylation is favored by 3.4 kcal/mol, and both findings are in agreement with the reported experimental observations. Most importantly, we concur that the barrier associated with the formation of carbocation 6 and its substituted analogues correlates with the C−H arylation outcomes. Furthermore, the β-arylation route remains unlikely for all the reaction pathways explored in this study.

Natural sesquiterpene quinone/quinols: chemistry, biological activity, and synthesis

“…55,[109][110][111][112] We noticed that compounds 200 and 201 were both reported as new compounds; however, they are isomers of the reported compounds in terms of the stereogenic centers at C-5, C-8, C-9, and C-10, and the double bond positions in the sesquiterpenoid part. 84,109 Nakijiquinones L, K, N, O, Q, and R (202)(203)(204)(205)(206)(207) were discovered from collections of Okinawan marine sponges of the family Spongiidae, and they possess unique side chains derived from amino acids. 113 The chromatographic fractionation of the extract from Spongia sp.…”

“…[201][202][203] Computational investigation proved that the regioselective g-arylation of cycloalkanols are more preferred by 3.4 kcal mol −1 when there are two methyl substituents on C-4 (Scheme 8). 204 4.1.3. Synthesis of dysidavarone A. Dysidavarone A (267) possesses an unprecedented "dysidavarane" carbon skeleton, which exhibits signicant PTP1B inhibitory, cytotoxicity, and anti-bacterial activity.…”

“…201–203 Computational investigation proved that the regioselective γ-arylation of cycloalkanols are more preferred by 3.4 kcal mol −1 when there are two methyl substituents on C-4 (Scheme 8). 204…”