TY - JOUR
T1 - New Insights in Frustrated Lewis Pair Chemistry with Azides
AU - Boom, Devin H.A.
AU - Jupp, Andrew R.
AU - Nieger, Martin
AU - Ehlers, Andreas W.
AU - Slootweg, J. Chris
PY - 2019/10/17
Y1 - 2019/10/17
N2 - The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.
AB - The geminal frustrated Lewis pair (FLP) tBu2PCH2BPh2 (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N3 and tBu−N3 are used. The reaction of 1 with Me3Si−N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.
KW - azides
KW - density functional calculations
KW - frustrated Lewis pairs
KW - heterocycles
KW - isocyanates
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U2 - 10.1002/chem.201902710
DO - 10.1002/chem.201902710
M3 - Article
C2 - 31497899
AN - SCOPUS:85073438451
VL - 25
SP - 13299
EP - 13308
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
SN - 0947-6539
IS - 58
ER -