13
38




— 3 —





— 4 —



(4113)








— 7 —
6 1917 9 1934
41 1966
51
41




[4116]

()

1
1Fries
e.g. 7, 8 , 9

10

NaBH4 alkanoyl, alkenyl, alkynyl Grignard Metal = MgX
Nu silyl enol ether vinyl ether indole

— 8 —
“”

2


— 9 —

— 10 —
26
arylsulfonyl



— 11 —

15
3

52→ 5354→ 55
56→57

— 12 —
58→59
260 MHz

(http://www.itsuu.or.jp)

(


(±)--Nominine 7
sanyoense Nakai“Nomi-base I”[1]
1982Kobusine 2 1
“Nominine” Figure 1[2]
Aconite alkaloid400
Atidane, Veatchane, Cycloveatchane, Aconitane,
Hetisan
1963[3] Nominine 1, Kobusine
2, Pseudokobusine 3Hetisine
[4] Hetisine

Atisine
[5]
Figure 1

4
A 74 [ i TBDMSOTf , Et3N
ii PdCl2Ph3P2 , Bu3SnF, LiCl ] 5→ 6
Figure 2
[ PdCl2Ph3P2 , Cs2CO3 , with or without Ph3P, in THF or toluene]

α
Hetisan7

11Figure 3 enone 1213N-C6
14C 15 161
40 (±) -1X
X
[1] E. Ochiai, T. Okamoto, S. Sakai, A. Saito, Yakugaku Zasshi 1956, 76, 1414-1418. [2] S. Sakai,
I. Yamamoto, K. Yamaguchi, H. Takayama, M. Ito, T. Okamoto, Chem. Pharm. Bull. 1982, 30, 4579-4582.
[3] W. Nagata, T. Sugasawa, M. Narisada, T. Wakabayashi, Y. Hayase, J. Am. Chem. Soc. 1963, 85, 2342-2343.
[4] H. Muratake, M. Natsume, Angew. Chem. Int. Ed. 2004, 43, 4646-4649. [5] M. Natsume, Chem. Pharm.
Bull. 1962, 10, 879-883. [6] H. Muratake, M. Natsume, H. Nakai, Tetrahedron 2004, 60, 11783-11803.

— 17 —


1987

APL
Am555S
RARcDNA
RAR
RXRRAR
LXRFXR
Figure 1
db/db




1. Kagechika, H.; Shudo. K Synthetic Retinoids: Recent Developments Concerning Structure and Clinical Utility.
J. Med. Chem., 2005, 48, in press.
2. Kagechika, H. Novel Synthetic Retinoids and Separation of the Pleiotropic Retinoidal Activities. Curr. Med.
Chem.2002, 9, 591- 608.
Figure 2
Figure 3