Synthesis of Angularly Substituted Trans-Fused Hydroindanes by Convergent Coupling of Acyclic Precursors
| Autor: | Mika Nakashige, Claudio Aquino, Glenn C. Micalizio, Valer Jeso, Haruki Mizoguchi, Xiayun Cheng |
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| Rok vydání: | 2014 |
| Předmět: |
Trimethylsilyl Compounds
Allylic rearrangement Annulation Stereochemistry Protonation 010402 general chemistry 01 natural sciences Biochemistry Catalysis Stereocenter Bridged Bicyclo Compounds Colloid and Surface Chemistry Cycloaddition Reaction Molecular Structure Enyne 010405 organic chemistry Chemistry Communication Regioselectivity Stereoisomerism General Chemistry Cycloaddition 0104 chemical sciences Cyclization Alkynes Intramolecular force Hydrocarbons Acyclic |
| Zdroj: | Journal of the American Chemical Society |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja504374j |
| Popis: | Angularly substituted trans-fused hydroindanes are now accessible by the direct and convergent union of trimethylsilyl (TMS)-alkynes with 4-hydroxy-1,6-enynes by a process that forges three C–C bonds, one C–H bond, and two new stereocenters. The annulation is proposed to proceed by initial formation of a Ti–alkyne complex (with a TMS-alkyne) followed by regioselective alkoxide-directed coupling with the enyne, stereoselective intramolecular cycloaddition, elimination of phenoxide, 1,3-metallotropic shift, and stereoselective protonation of the penultimate allylic organometallic intermediate. Several examples are given to demonstrate the compatibility of this reaction with substrates bearing aromatic and aliphatic substituents, and an empirical model is presented to accompany the stereochemical observations. |
| Databáze: | OpenAIRE |
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