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oai:figshare.com:article/33966284 2026-09-22T16:06:48Z category_1 category_4 category_7 category_12 category_13 category_21 category_39 category_64 category_133 portal_63 item_type_3 month_year_09_2026

Diastereodivergent Access to cis,cis- and cis,trans-Angular Triquinanes: Total Synthesis of (±)-Arnicenone Chia-Hao Liu (564516) Hung-Tse Huang (1562035) Han-Jung Li (2071954) Shubham A. Dighe (25090922) Deng-Lian Hou (20630547) Li-Yun Wu (489826) Yu-Wen Huang (210830) Biophysics Biochemistry Medicine Cell Biology Genetics Biotechnology Ecology Cancer Plant Biology multiple contiguous stereocenters initial spirocyclization governs dft calculations indicate common allene precursors allene precursor reversed accessed via photochemical (±)- arnicenone via providing direct access >- fused triquinanes >- angular triquinane >- angular triquinanes oxidative ring expansion danheiser annulation product 1 </ sup angular triquinanes oxidative ring danheiser annulation stereodivergent access stereocontrolled access diastereodivergent access trans </ cis </ unified platform two approaches total synthesis synthetic utility stereochemical outcome results establish promoted intramolecular observed diastereodivergence lewis acid important class expansion pathway alternative synthesis Angular triquinanes constitute an important class of polycyclic natural products characterized by compact, angularly fused ring systems and multiple contiguous stereocenters. Herein, we report a diastereodivergent strategy for stereocontrolled access to both cis,trans- and cis,cis-angular triquinanes from common allene precursors. The cis,trans-fused triquinanes were constructed through a Lewis acid-promoted intramolecular [3+2] Danheiser annulation, whereas the complementary cis,cis frameworks were accessed via photochemical [2+2] cycloaddition followed by oxidative ring expansion. Notably, substitution at the R1 position of the allene precursor reversed the diastereoselectivity of the [3+2] annulation, providing direct access to a cis,cis-angular triquinane. DFT calculations indicate that the initial spirocyclization governs both the reactivity and stereochemical outcome of the [3+2] pathway, with substrate-dependent steric interactions accounting for the observed diastereodivergence. The synthetic utility of this strategy was demonstrated through the total synthesis of (±)-arnicenone via the [2+2] cycloaddition/oxidative ring-expansion pathway, while an alternative synthesis from the cis,cis-[3+2] Danheiser annulation product further highlights the complementary nature of the two approaches. Together, these results establish a unified platform for stereodivergent access to angular triquinanes and their application to complex natural product synthesis. 2026-09-22T00:00:00Z Dataset Dataset 10.1021/jacs.6c09019.s001 https://figshare.com/articles/dataset/Diastereodivergent_Access_to_cis_cis-_and_cis_trans-Angular_Triquinanes_Total_Synthesis_of_-Arnicenone/33966284 CC BY-NC 4.0