TY - JOUR
T1 - Rearrangement of Hydroxylated Pinene Derivatives to Fenchone-Type Frameworks
T2 - Computational Evidence for Dynamically-Controlled Selectivity
AU - Blümel, Marcus
AU - Nagasawa, Shota
AU - Blackford, Katherine
AU - Hare, Stephanie R.
AU - Tantillo, Dean J.
AU - Sarpong, Richmond
N1 - Funding Information:
This work was supported by the National Science Foundation (NSF, CHE-1566430 to R.S. and CHE-1565933 and CHE-030089 [computational support via XSEDE] to D.T.).
PY - 2018/7/25
Y1 - 2018/7/25
N2 - An acid-catalyzed Prins/semipinacol rearrangement cascade reaction of hydroxylated pinene derivatives that leads to tricyclic fenchone-type scaffolds in very high yields and diastereoselectivity has been developed. Quantum chemical analysis of the selectivity-determining step provides support for the existence of an extremely flat potential energy surface around the transition state structure. This transition state structure appears to be ambimodal, i.e., the fenchone-type tricyclic scaffolds are formed in preference to the competing formation of a bornyl (camphor-type) skeleton under dynamic control via a post-transition state bifurcation (PTSB).
AB - An acid-catalyzed Prins/semipinacol rearrangement cascade reaction of hydroxylated pinene derivatives that leads to tricyclic fenchone-type scaffolds in very high yields and diastereoselectivity has been developed. Quantum chemical analysis of the selectivity-determining step provides support for the existence of an extremely flat potential energy surface around the transition state structure. This transition state structure appears to be ambimodal, i.e., the fenchone-type tricyclic scaffolds are formed in preference to the competing formation of a bornyl (camphor-type) skeleton under dynamic control via a post-transition state bifurcation (PTSB).
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U2 - 10.1021/jacs.8b05804
DO - 10.1021/jacs.8b05804
M3 - Article
C2 - 29968475
AN - SCOPUS:85049657241
VL - 140
SP - 9291
EP - 9298
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 29
ER -