TY - JOUR
T1 - Stereoselectivity of the captodative alkenes 1-acetylvinyl arenecarboxylates in Diels-Alder reactions with cyclic dienes and stereospecific rearrangement of their bicyclo[2.2.n] α-ketol adducts
AU - Aguilar, Raúl
AU - Santoyo, Blanca M.
AU - Zárate-Zárate, Daniel
AU - Vázquez, Miguel A.
AU - Padilla, Rosa M.
AU - Jiménez-Vázquez, Hugo A.
AU - Tamariz, Joaquín
N1 - Publisher Copyright:
© 2017 The Authors
PY - 2020/1
Y1 - 2020/1
N2 - Captodative alkene 1-acetylvinyl p-nitrobenzenecarboxylate 1a was evaluated for its reactivity and stereoselectivity with cyclohexadiene (10) in Diels-Alder reactions, showing exclusive endo preference. The two hydrolyzed products of the endo and the exo adducts obtained from the Diels-Alder cycloaddition between 1a and cyclopentadiene (7) were 8b and 9b. When treated with mCPBA, a ring expansion took place to stereospecifically yield the novel 3-oxatricyclo[3.3.1.02,4]nonanone acyloins 15 and 16, respectively. In the case of the α-ketol bicyclo[2.2.2]octanes 11b and 12b, the epoxidation/Baeyer-Villiger cascade process was preferred, resulting in the syn ketoepoxide 19b from each isomer. A synthetic application of this kind of transformation was carried out by reacting ketols 8b and 9b with an excess of mCPBA through a five-step cascade process to yield the bicyclic lactone 27 as a potential precursor of racemic β-carbaxylose.
AB - Captodative alkene 1-acetylvinyl p-nitrobenzenecarboxylate 1a was evaluated for its reactivity and stereoselectivity with cyclohexadiene (10) in Diels-Alder reactions, showing exclusive endo preference. The two hydrolyzed products of the endo and the exo adducts obtained from the Diels-Alder cycloaddition between 1a and cyclopentadiene (7) were 8b and 9b. When treated with mCPBA, a ring expansion took place to stereospecifically yield the novel 3-oxatricyclo[3.3.1.02,4]nonanone acyloins 15 and 16, respectively. In the case of the α-ketol bicyclo[2.2.2]octanes 11b and 12b, the epoxidation/Baeyer-Villiger cascade process was preferred, resulting in the syn ketoepoxide 19b from each isomer. A synthetic application of this kind of transformation was carried out by reacting ketols 8b and 9b with an excess of mCPBA through a five-step cascade process to yield the bicyclic lactone 27 as a potential precursor of racemic β-carbaxylose.
KW - 1-Acetylvinyl p-nitrobenzoyloxy
KW - Captodative alkenes
KW - Cascade process
KW - mCPBA
KW - α-Keto carbinols
KW - α-Ketol rearrangement
UR - http://www.scopus.com/inward/record.url?scp=85029412239&partnerID=8YFLogxK
U2 - 10.1016/j.arabjc.2017.08.008
DO - 10.1016/j.arabjc.2017.08.008
M3 - Artículo
SN - 1878-5352
VL - 13
SP - 900
EP - 915
JO - Arabian Journal of Chemistry
JF - Arabian Journal of Chemistry
IS - 1
ER -