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Development and application of
cage type amino alcohol organocatalyst
v°_ 1Fv˺M 2FÎ]¼ 1FHK~c 1Fiª 3Fny¬q 4FJÉ^L 1
Ós¾{mÏ{ 1F\À{m 2F\mÏ£|m«6 3F\½m 4Ô
h+B=+C1GCÕÊxÁpIÇPqU'¸)&[d
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steric influence
3=CAC;E+B=+C1GC 1 1) Õ¯Q¨z%
Ph
Ph
mh 2+3=CAC;EÑ)ÕÑ
OH
V-;BEÆP¸&®²_q)f*
N H
H
non-covalent
&Ö$ÕTÌÕ¯QXÆP»Ð
enamine
hydrogen
formation
site
bonding site
[²jÕ$²µdÆPÈj)&
2-azanorbornane
$ÕWqÁpÒ¸)!'
organocatalyst 1
& (Scheme 1)Ö$'Õh+B=+C1
Scheme 1
GC)WqÁp¦a
kgSwÖ
«Õh+B=+C1GCWqÁp¸)$
&)©¨ 2+3=CAC;EÁp 1 )¦&d[r¨¦I+C:G
Ca
)ÂÖ
O
µÕÁp 1 )¦&,2
O
O
catalyst
1
HO
7E 2 40D?/2=E 3 (20 mol%)
+
O
# p<9D@E5+C8>: 4
O
TFA (10 mol%)
N
N
toluene
H
40D?/2=E 3 '
H
rt, 24 h
2
3
[2S, 3R]-5
'I+C:GCa
Õ
ºo[rb¢-;E7.Å
OH
O
O
catalyst 1
© ¨ & ¥ 5 (84%,
(15 mol%)
+
3
38% ee) # 6 (50%, 37% ee) H
brine
NO2
rt, 48 h
NO2
$'ÕÁp 1 WqÁp
[1R, 2R]-6
4
¸)&$
Scheme 2
(Scheme 2)Ö
Áp 1 #ÄuQ)¦'$a
óÕ#I DielsAlder a
2,3) I¤[OZa
&Áp¦!Rkg&Ö
×`¶¡Ø
1ÔH. Nakano, N. Kumagai, H. Matsuzaki, C. Kabuto, H. Hongo, Tetrahedron: Asymmetry, 1997, 8,
13911401.
2ÔH. L. Cui, F. Tanaka, Chem. Eur. J., 2013, 19, 62136216.
6216.
3ÔY. Kohari, Y. Okuyama, E. Kwon, T. Furuyama, N. Kobayashi, T. Otuki, J. Kumagai, C. Seki, K.
Uwai, G. Dai, T. Iwasa, H. Nakano, J. Org. Chem., 2014, 79, 95009511.
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