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(-) - Pinnaic Acid (TKGP 110129) H. Arimoto, D. Uemura: Activity

(–)-Pinnaic acid is a natural product that inhibits cPLA2. Key reactions in its total synthesis include (A) Pd-catalyzed cyclization, (B) hydrogenation-cyclization, and (C) cross-olefin metathesis. The synthesis involves multiple protection, oxidation, reduction, and deprotection steps to transform the starting materials into the target molecule (–)-pinnaic acid sodium salt.

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Percival Galahad
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86 views2 pages

(-) - Pinnaic Acid (TKGP 110129) H. Arimoto, D. Uemura: Activity

(–)-Pinnaic acid is a natural product that inhibits cPLA2. Key reactions in its total synthesis include (A) Pd-catalyzed cyclization, (B) hydrogenation-cyclization, and (C) cross-olefin metathesis. The synthesis involves multiple protection, oxidation, reduction, and deprotection steps to transform the starting materials into the target molecule (–)-pinnaic acid sodium salt.

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Percival Galahad
Copyright
© © All Rights Reserved
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(–)-Pinnaic acid (TKGP 110129) H. Arimoto, D.

Uemura1)

HO2C
HN
HO Cl OH

Activity Inhibition of cPLA2（細胞質型ホスホリパーゼ A2 阻害活性）

(A) Pd-TMM [3+2] cyclization, (B) tandem hydrogenation-cyclization,


Key Reactions
(C) cross-olefin-metathesis

1) H2C=CHCH2OH
B-117, C-49 OPMP
1) O3 ?, toluene; O
AcOH-EtOAc CO2Allyl PMPO(CH2)2I ?

O 2) H2C=CHCH2OH CO2Allyl 2) aq HCl CO2Allyl CH3CN


?

OPMP
OPMP OPMP ? 1) O3; Me2S
O O
? Al2O3 H 2) ?
O N
Pd(OAc)2 CH2Cl2 3) NaBH3CN
(i-PrO)3P cat TsOH
(A) C-14

OPMP 1) TBDPSCl
1) CbzCl OPMP Et3N OH
H ? DMAP
O N CbzHN CbzHN
2) LiBH4 2) ?
aq CH3CN
HO TBDPSO

TBSO

O TBSO
1) SO3—Pyr, DMSO B-99
Et3N 1) ?, ? CF3CO N
2) O O 2) TFAA, i-Pr2NEt
TBSO P(OMe)2 CbzHN
3
ClCH2CH2Cl
TBDPSO
Et3N, ?, THF
TBDPSO
EtO2C
?
1) PPTS, EtOH CF3CO N N CF3CO N
CF3CO +
2) ? Hoveyda-Grubbs II
n-Bu3P;
mCPBA TBDPSO (C) TBDPSO
TBDPSO
1 2

###

TBDPSCl ?
Et3N, DMAP TBDPSO LiBr; HO IBX O
OH
TBDPSO TBDPSO
CH2Cl2 acrolein EtOAc

(R)-Me-CBS ? TBSOTf
? HO THF; Et3N
TBDPSO Cl OH TBDPSO Cl OTBS
TBDPSO
THF NCS CH2Cl2
2

###

EtO2C EtO2C
1) HF—Pyr 2
N CF3CO N
1 CF3CO TBDPSO Cl OTBS
2) ? Grubbs II
?; mCPBA
(C)

Na O2C
1) HF—Pyr
HN
HO Cl OH
2) NaBH4;
aq NaOH

(–)-Pinnaic acid sodium salt

Reference:
1) S. Xu, H. Arimoto, D. Uemura, Angew. Chem., Int. Ed., 46, 5746 (2007)

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