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- W4206119429 abstract "Abstract Chiral trans ‐hydrindanes (bicyclo[4.3.0]nonanes) are important building blocks of polycyclic natural products. In order to access 5/6/5‐ and 5/6/6‐carbotricyclic scaffolds scope and limitation of [4+2] cycloadditions of tetrahydroindanones with various dienes were studied. Cyclopentadiene gave a tetracylic endo ‐( R,R )‐diastereomer under acid‐catalysis, whereas thermal conditions provided the endo ‐( S,S )‐diastereomer with the opposite diastereofacial selectivity. The stereodivergent outcome was rationalized by high‐level quantum‐chemical computations which revealed the acid‐catalysis to be a kinetically controlled reaction and the thermal cycloaddition to be under thermodynamic control. Stereochemical assignment of the cycloadducts was facilitated by conversion of the 1,3‐dicarbonyls with BF 3 ⋅ OEt 2 into BF 2 ‐chelate complexes. Subsequent thermal Diels‐Alder reaction of BF 2 ‐ or BBN‐chelates (from 9‐BBN‐OTf) gave endo / exo ‐mixtures of the ( R,R )‐ and ( S,S )‐diastereomers, while more elevated temperatures yielded primarily the endo / exo ‐( S,S )‐diastereomers. Thermal [4+2] cycloadditions with 2,3‐dimethylbutadiene proceeded with lower diastereoselectivity as the reaction was kinetically controlled according to calculations. Attempted Diels‐Alder‐reactions with furan gave furyl‐substituted indanones rather than cycloadducts." @default.
- W4206119429 created "2022-01-25" @default.
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- W4206119429 creator A5090471164 @default.
- W4206119429 date "2022-02-22" @default.
- W4206119429 modified "2023-09-27" @default.
- W4206119429 title "Chasing polycyclic natural products: 5/6/5‐ or 5/6/6‐carbotricyclic scaffold construction via stereodivergent Diels‐Alder reaction of chiral hydrindanes and their boron complexes" @default.
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