Jump to main content
Jump to site search

Issue 2, 2014
Previous Article Next Article

Tactics for probing aryne reactivity: mechanistic studies of silicon–oxygen bond cleavage during the trapping of (HDDA-generated) benzynes by silyl ethers

Author affiliations

Abstract

We report mechanistic aspects of the trapping of thermally (HDDA) generated benzyne derivatives by pendant silyl ether groups, which results in net insertion of the pair of benzyne Csp-hydribized carbon atoms into the silicon–oxygen sigma bond. Cross-over experiments using symmetrical, doubly labeled bis-silyl ether substrates established that the reaction is unimolecular in nature. Competition experiments involving either intramolecular or intermolecular dihydrogen transfer clock reactions (from within a TIPS isopropyl group or cyclooctane, respectively) vs. the silyl ether cyclization were used to gain additional insights. We evaluated effects of the steric bulk of the silyl ether trapping group and of the ring-size of the cyclic ether being formed (furan vs. pyran). These types of competition experiments allow the relative rates of various product-determining steps to be determined. This previously has only rarely been possible because aryne formation is typically rate-limiting, making it challenging to probe the kinetics of subsequent trapping reactions. Solvent effects (polarity of the medium) and computational studies were used to probe the question of stepwise vs. concerted pathways for the Si–O insertion.

Graphical abstract: Tactics for probing aryne reactivity: mechanistic studies of silicon–oxygen bond cleavage during the trapping of (HDDA-generated) benzynes by silyl ethers

Back to tab navigation

Supplementary files

Publication details

The article was received on 30 okt. 2013, accepted on 02 des. 2013 and first published on 02 des. 2013


Article type: Edge Article
DOI: 10.1039/C3SC53014K
Author version available: Download Author version (PDF)
Citation: Chem. Sci., 2014,5, 545-550
  •   Request permissions

    Tactics for probing aryne reactivity: mechanistic studies of silicon–oxygen bond cleavage during the trapping of (HDDA-generated) benzynes by silyl ethers

    T. R. Hoye, B. Baire and T. Wang, Chem. Sci., 2014, 5, 545
    DOI: 10.1039/C3SC53014K

Search articles by author

Spotlight

Advertisements