Synthesis and Reactions of Pentacycloundecane Derivatives Related to Cookson’s Dione

Abstract

In this study, a pentacyclic keto-olefin was treated with thallium(III) nitrate trihydrate, resulting in the formation of mono ring-expanded product. However, when the corresponding dialkene was treated with thallium(III) nitrate trihydrate, an unexpected ring-closure product was obtained instead of the expected double ring-expanded product. The use of the Tebbe reagent facilitated the olefination of hindered and enolizable cage dione derivatives, converting both keto moieties into methylene groups and forming the desired diolefin. Notably, conventional Wittig reagents proved to be ineffective in the olefination sequence with cage diones.

Key words

Diels–Alder reaction - photocycloaddition - pentacycloundecanes - Peterson reaction - thallium trinitrate - ring expansion

Publication History

Received: 25 May 2024

Accepted after revision: 12 June 2024

Accepted Manuscript online:
28 June 2024

Article published online:
17 July 2024

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• 52 Diolefination of Cage Diones with the Tebbe Reagent; General Procedure The Tebbe reagent (4 equiv) was added dropwise to a precooled solution of the appropriate cage diol (0.78–1.14 mmol) in dry THF at 0 ℃ under N₂, and the mixture was stirred at r.t. for 2 h. When the reaction was complete (TLC), 5% aq NaHCO₃ was added and the mixture was extracted with EtOAc. The organic layer was washed with brine (20 mL), dried (Na₂SO₄), filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, 1% EtOAc–PE). 17 Prepared according to the general procedure from cage diol 16 (200 mg, 1.14 mmol) to give a colorless liquid; yield: 148 mg (74%). IR (CH₂Cl₂): 2980, 2882, 1740, 1668 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.60 (d, J = 10.9 Hz, 2 H), 2.19 (s, 4 H), 2.26 (d, J = 12.9 Hz, 2 H), 2.37 (s, 2 H), 2.63 (s, 2 H), 4.70 (s, 2 H), 4.84 (s, 2 H). ¹³C NMR (100.6 MHz, CDCl₃): δ = 155.34, 106.17, 54.46, 48.88, 42.11, 33.74, 32.49. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₃H₁₅: 171.1166; found: 171.1167.