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various functional groups such as halogen, ester, amide,
phosphonate, and nitro groups.
To highlight the synthetic utility of this transformation, fur-
ther transformation of the chiral 3,4-dihydroisoquinolinones
obtained from this process was undertaken (Scheme 2). The
amide carbonyl group and the alkene moiety in 3aa could be
selectively reduced to afford 4 and 5, respectively, in good
yields without loss of the optical purity. Smooth removal of
the N-Ts group led to NH-free 3,4-dihydroisoquinolinones,
which could be transformed into 6 by allylation. Then, a
metathesis reaction of 6 was carried out to form a chiral tricy-
clic heterocycle, dihydropyrrolo[1,2-b]isoquinolin-5(3H)-one
7 without any racemization.
In summary, we have developed a Pd(II)-catalyzed asym-
metric synthesis of 3,4-dihydroisoquinolinones through a
one-pot C─C and C─N bonds formation between N-Ts-
benzamides and 1,3-dienes using a chiral PyOX-type ligand.
This protocol features regio- and stereoselective synthesis of
chiral 3,4-dihydroisoquinolinones from readily available
starting materials, mild neutral reaction conditions in air,
broad substrate scope, and good functional group tolerance.
Further elaboration of the resulting 3,4-dihydroisoquinolinone
products provided access to diverse chiral N-heterocycles.
Acknowledgments. This work was supported by both the
Basic Science Research Program and NanoÁMaterial Technol-
ogy Department Program through the National Research Foun-
dation of Korea (NRF) funded by the Korea government
(MSIT) (Nos. 2012M3A7B4049644, 2018R1A2A2A05018392,
and 2014-011165).
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Supporting Information. Additional supporting informa-
tion may be found online in the Supporting Information
section at the end of the article.
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Bull. Korean Chem. Soc. 2021, Vol. 42, 521–524
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