Abstract
2-Silicon-substituted 1,3-dienes containing non transferrable groups known to promote transmetallation were prepared by Grignard chemistry and enyne metathesis. These dienes participated in one pot metathesis/Diels-Alder reactions in regio- and diastereoselective fashions. Electron-rich alkenes showed the fastest rates in metathesis reactions, and ethylene, a commonly used metathesis promoter slowed enyne metathesis. 2-Pyridyldimethylsilyl and 2-thienyldimethylsilyl substituted Diels-Alder cycloadducts participated in cross-coupling chemistry and the 2-thienyldimethylsilyl substituted cycloadducts underwent cross-coupling under very mild reaction conditions.
Highlights
We have been interested in the preparation and reaction chemistry of metal-substituted dienes for over 20 years
We prepared a number of transition metal-substituted dienes [1,2] for these studies but, more recently, we have been interested in the investigation of silicon- and boron-substituted dienes [3,4,5,6,7]
We have reported the preparation of 2-silicon-substituted 1,3-butadienes by a variety of synthetic routes and demonstrated that they could be used in sequential Diels-Alder/cross-coupling reactions [8,9,10,11,12,13]
Summary
We have been interested in the preparation and reaction chemistry of metal-substituted dienes for over 20 years. We prepared a number of transition metal-substituted dienes [1,2] for these studies but, more recently, we have been interested in the investigation of silicon- and boron-substituted dienes [3,4,5,6,7]. We have reported the preparation of 2-silicon-substituted 1,3-butadienes by a variety of synthetic routes and demonstrated that they could be used in sequential Diels-Alder/cross-coupling reactions [8,9,10,11,12,13]. We report the preparation of new 2-silicon-substituted 1,3-dienes containing silicon substituents known to promote transmetallation While the new chemistry disclosed here was not aimed at cis-clerodane synthesis targets, we believe it can be used to access those biologically-significant core structures [14]
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
