The Mechanism of Copper-Catalyzed Trifunctionalization of Terminal Allenes

Cited 0 time in webofscience Cited 0 time in scopus
  • Hit : 16
  • Download : 0
A highly selective copper-catalyzed trifunctionalization of allenes has been established based on diborylation/cyanation with bis(pinacolato)diboron (B(2)pin(2)) and N-cyano-N-phenyl-p-toluenesulfonamide (NCTS). The Cu-catalyzed trifunctionalization of terminal allenes is composed of three catalytic reactions (first borocupration, electrophilic cyanation, and second borocupration) that provide a densely functionalized product with regio-, chemo- and diastereoselectivity. Allene substrates have multiple reaction-sites, and the selectivities are determined by the suitable interactions (e.g., electronic and steric demands) between the catalyst and substrates. We employed DFT calculations to understand the cascade copper-catalyzed trifunctionalization of terminal allenes, providing densely-functionalized organic molecules with outstanding regio-, chemo- and diastereoselectivity in high yields. The selectivity challenges presented by cumulated pi-systems are addressed by systematic computational studies; these give insight to the catalytic multiple-functionalization strategies and explain the high selectivities that we see for these reactions.
Publisher
WILEY-V C H VERLAG GMBH
Issue Date
2019-07
Language
English
Article Type
Article; Proceedings Paper
Citation

CHEMISTRY-A EUROPEAN JOURNAL, v.25, no.40, pp.9456 - 9463

ISSN
0947-6539
DOI
10.1002/chem.201900673
URI
http://hdl.handle.net/10203/267450
Appears in Collection
CH-Journal Papers(저널논문)
Files in This Item
There are no files associated with this item.

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0