10.1002/asia.201900995
Chemistry - An Asian Journal
COMMUNICATION
butadiene (entries 16 and 17), which has no alkoxy group at C2(1),
because the C intermediate cannot be formed via an interaction with
Acknowledgements
B.
The Danishefsky-Kitahara diene possessing C2(1)OCH3
This work was aided by JSPS KAKENHI Grant Number
JP16H02274, JP18H04250, and JP17H17415, the Platform Project
for Supporting Drug Discovery and Life Science Research funded by
Japan Agency for Medical Research and Development (AMED;
Grant Number JP18am0101099), an Advanced Catalytic
Transformation program for Carbon utilization (ACT-C; Grant
Number JPMJCR12YC) from Japan Science and Technology
Agency (JST), and The Sumitomo Foundation.
smoothly reacted with 1a to give the qADA adduct with a 96:4 er
(entry 18). Introduction of a CH3 substituent at C2(4) of 2a
simultaneously constructed four stereogenic centers with high
selectivity in combination with various 1a-type dienophiles (entries
19–24).
C2(1)OCH2OCH3 (OMOM) (entries 20, 22, and 24).[11] qADA
adducts obtained in the reaction of 1a with
The C2(1)OCH3 group could be replaced with
a
C2(1)OCH3/C2(4)CH3- or C2(1)OMOM/C2(4)CH3-substituted
diene easily underwent elimination; therefore, the reaction mixture
was treated with silica gel to convert the adducts to the
corresponding hexadiene product with a >99:1 er in 85–88% yields
(entries 21 and 22). A diene bridged between C2(1) and C2(4) was
used to quantitatively furnish the tricyclic qADA adduct with a 99:1
er (entry 25). When a C1(5)CH3/C1(6)CH3-substituted dienophile
was used in combination with a C2(1)OCH3/C2(4)CH3-substituted
diene, the site selectivity for the C1(5)=C1(6)/C1(2)=C1(3) double
bond was lost to provide two enantiomerically pure qADA adducts 3
and 5 (entry 26). In the corresponding C1(6)CH3/C2(4)CH3-
Keywords: Asymmetric catalysis • Diels-Alder reaction •
Homogeneous catalyst • sp2N bidentate ligand • Zinc
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In summary, we have discovered that a Zn(II) complex of a
bisamidine-type sp2N-based bidentate ligand, (R,R)-Naph-diPIM-
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quaternary carbon centers can be installed. This first high
performance qADA should provide chemists in the fields of total
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synthesis, medicinal chemistry, and process chemistry with
a
powerful tool for asymmetric syntheses of pharmaceutically
important complex natural and unnatural products.[1]
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provide important guidelines for the design of various chiral key
intermediates and future chiral catalysts.
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[25] For details, see supporting information.
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