Diastereoselective Formal [5+2] Cycloaddition of Diazo Arylidene Succinimides-Derived Rhodium Carbenes and Aldehydes : A Route to 2-Benzoxepines. / Inyutina, Anna; Kantin, Grigory; Dar'In, Dmitry; Krasavin, Mikhail.
In: Journal of Organic Chemistry, Vol. 86, No. 19, 01.10.2021, p. 13673–13683.Research output: Contribution to journal › Article › peer-review
}
TY - JOUR
T1 - Diastereoselective Formal [5+2] Cycloaddition of Diazo Arylidene Succinimides-Derived Rhodium Carbenes and Aldehydes
T2 - A Route to 2-Benzoxepines
AU - Inyutina, Anna
AU - Kantin, Grigory
AU - Dar'In, Dmitry
AU - Krasavin, Mikhail
N1 - Publisher Copyright: © 2021 American Chemical Society.
PY - 2021/10/1
Y1 - 2021/10/1
N2 - We report on a facile method for the preparation of 2-benzoxepine derivatives as a result of Rh(II)-catalyzed decomposition of diazo arylidene succinimides in the presence of aldehydes. The process is thought to involve the formation of styryl carbonyl ylide which undergoes 1,7-electrocyclization and subsequent 1,5-hydrogen shift. In some cases, the competition of the target reaction and [3+2] dipolar cycloaddition of the intermediate carbonyl ylide to another molecule of diazo substrate was observed. Generally, the desired 2-benzoxepines were isolated in good to high yields and high diastereoselectivity. The developed original approach toward a 2-benzoxepine core via formal [5+2] cycloaddition of styryl carbenoids and aldehydes significantly expands the arsenal of synthetic methods for producing this scaffold.
AB - We report on a facile method for the preparation of 2-benzoxepine derivatives as a result of Rh(II)-catalyzed decomposition of diazo arylidene succinimides in the presence of aldehydes. The process is thought to involve the formation of styryl carbonyl ylide which undergoes 1,7-electrocyclization and subsequent 1,5-hydrogen shift. In some cases, the competition of the target reaction and [3+2] dipolar cycloaddition of the intermediate carbonyl ylide to another molecule of diazo substrate was observed. Generally, the desired 2-benzoxepines were isolated in good to high yields and high diastereoselectivity. The developed original approach toward a 2-benzoxepine core via formal [5+2] cycloaddition of styryl carbenoids and aldehydes significantly expands the arsenal of synthetic methods for producing this scaffold.
KW - CARBONYL YLIDE REACTIONS
KW - DIOSCOREALIDE B
KW - VINYL
KW - DIHYDROFURANS
KW - BENZYLIDENE
KW - METABOLITES
KW - DERIVATIVES
UR - http://www.scopus.com/inward/record.url?scp=85115954885&partnerID=8YFLogxK
U2 - 10.1021/acs.joc.1c01710
DO - 10.1021/acs.joc.1c01710
M3 - Article
AN - SCOPUS:85115954885
VL - 86
SP - 13673
EP - 13683
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 19
ER -
ID: 86412666