TY - JOUR
T1 - Insertion reactions of silacyclopropanes
T2 - Evidence for a radical-based mechanism
AU - Rotsides, Christina Z.
AU - Woerpel, K. A.
N1 - Funding Information:
This research was supported by the National Science Foundation (CHE-1362709). NMR spectra collected using the TCI CryoProbe at NYU were supported by an S10 grant from the National Institutes of Health (OD016343). We thank Dr. Chin Lin (NYU) for his assistance with NMR spectroscopy and mass spectrometry. We thank Jillian Sanzone (NYU) for insightful discussions.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/9/26
Y1 - 2016/9/26
N2 - Silacyclopropanes reacted rapidly and selectively with p-benzoquinones to provide oxasilacyclopentanes. Ring-expansion products were observed in the absence of a catalyst, elevated temperatures, or irradiation. As substitution was increased on the silacyclopropane ring, improved stereoselectivity was observed. In some cases, the regiochemistry was controlled depending on the extent of stabilization of the reactive intermediates involved. A radical clock experiment, along with stereochemical studies, confirmed that radical intermediates were involved in the ring-expansion reaction. The scope of this radical reaction was expanded to include dienones, aryl aldehydes, and electron-deficient enones in addition to benzoquinones. In the case of aryl aldehydes and electron-deficient enones, the radical reaction can be used to generate silylenes from silacyclopropanes.
AB - Silacyclopropanes reacted rapidly and selectively with p-benzoquinones to provide oxasilacyclopentanes. Ring-expansion products were observed in the absence of a catalyst, elevated temperatures, or irradiation. As substitution was increased on the silacyclopropane ring, improved stereoselectivity was observed. In some cases, the regiochemistry was controlled depending on the extent of stabilization of the reactive intermediates involved. A radical clock experiment, along with stereochemical studies, confirmed that radical intermediates were involved in the ring-expansion reaction. The scope of this radical reaction was expanded to include dienones, aryl aldehydes, and electron-deficient enones in addition to benzoquinones. In the case of aryl aldehydes and electron-deficient enones, the radical reaction can be used to generate silylenes from silacyclopropanes.
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U2 - 10.1021/acs.organomet.6b00469
DO - 10.1021/acs.organomet.6b00469
M3 - Article
AN - SCOPUS:84989345512
VL - 35
SP - 3132
EP - 3138
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 18
ER -