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Rapid Formation of Hindered Cores

Using an Oxidative Prins Process


Jean-Christophe Andrez, Marc-Andre´ Giroux, Jessica Lucien, Sylvain Canesi*
Organic Letter, 2010, 12, 4368-4371

Aayushi Chatterji
Literature Presentation
Sharma Lab, The Univ. of Oklahoma
February 23, 2019
Classic Prins and Oxidative Prins Reaction

Prins transformation:

Chem. Weekbald 1919, 16, 1072

Oxidative Prins Reaction:


Canesi’s Report on Oxidative Prins Process

R R
q Nucleophile addition PhI(OAc) 2
(PIDA)
HO O
0 °C, 2 min
R R Nu

entry R solvent Nu yield (%)


a H HFIP OCH(CF3)3 61
b H HFIP/DCM Cl 57
c Br HFIP/DCM Cl 73
d H TFA OCOCF3 62
e H HFIP/PhH Ph 50
Oxidative Prins Process

q Effect of substituents on 1 and 2 positions

q Contiguous quaternary carbon center formation

R R
PhI(OAc) 2
HFIP/DCM
HO O
0 °C, 2 min
R R Cl

R = H 78%
R = Br 86%
Oxidative Prins Process

q Ring contraction (substitution at 3 position)


Oxidative Prins Process

q Reaction with protected alkyne

q Application of Oxidative Prins Process: Spirodienone synthesis