References
1a </A>
Nose H.
Seki A.
Yaguchi T.
Hosoya A.
Sasaki T.
Hoshoko S.
Shomura T.
J. Antibiot.
2000,
53:
33
1b </A>
Sasaki T.
Nose H.
Hosoya A.
Yoshida S.
Kawaguchi M.
Watanabe T.
Usui T.
Ohtsuka Y.
Shomura T.
Takano S.
Tatsuta K.
J. Antibiot.
2000,
53:
38
<A NAME="RD36109ST-2">2 </A>
Tatsuta K.
Takano S.
Ikeda Y.
Nakano S.
Miyazaki S.
J. Antibiot.
1999,
52:
1146
3a </A>
Barry CSJ.
Crosby StR.
Harding JR.
Hughes RA.
King CD.
Parker GD.
Willis CL.
Org.
Lett.
2003,
5:
2429
3b </A>
Yang X.-F.
Mague JT.
Li C.-J.
J.
Org. Chem.
2001,
66:
739
3c </A>
Aubele DL.
Wan S.
Floreancig PE.
Angew. Chem. Int. Ed.
2005,
44:
3485
3d </A>
Barry CS.
Bushby N.
Harding JR.
Willis CS.
Org.
Lett.
2005,
7:
2683
3e </A>
Cossey KN.
Funk RL.
J.
Am. Chem. Soc.
2004,
126:
12216
3f </A>
Crosby SR.
Harding JR.
King CD.
Parker GD.
Willis CL.
Org. Lett.
2002,
4:
3407
3g </A>
Marumoto S.
Jaber JJ.
Vitale JP.
Rychnovsky SD.
Org.
Lett.
2002,
4:
3919
3h </A>
Kozmin SA.
Org. Lett.
2001,
3:
755
3i </A>
Jaber JJ.
Mitsui K.
Rychnovsky SD.
J. Org. Chem.
2001,
66:
4679
3j </A>
Kopecky DJ.
Rychnovsky SD.
3k </A>
Rychnovsky SD.
Thomas CR.
Org.
Lett.
2000,
2:
1217
3l </A>
Rychnovsky SD.
Yang G.
Hu Y.
Khire UR.
J. Org. Chem.
1997,
62:
3022
3m </A>
Su Q.
Panek JS.
J. Am. Chem. Soc.
2004,
126:
2425
3n </A>
Yadav JS.
Reddy BVS.
Sekhar KC.
Gunasekar D.
Synthesis
2001,
885
3o </A>
Yadav JS.
Reddy BVS.
Reddy MS.
Niranjan N.
J.
Mol. Catal. A: Chem.
2004,
210:
99
3p </A>
Yadav JS.
Reddy BVS.
Reddy MS.
Niranjan N.
Prasad AR.
Eur. J. Org. Chem.
2003,
1779
4a </A>
Yadav JS.
Reddy MS.
Rao PP.
Prasad AR.
Tetrahedron
Lett.
2006,
47:
4397
4b </A>
Yadav JS.
Reddy MS.
Prasad AR.
Tetrahedron Lett.
2006,
47:
4937
4c </A>
Yadav JS.
Reddy MS.
Prasad AR.
Tetrahedron Lett.
2005,
46:
2133
4d </A>
Yadav JS.
Reddy MS.
Prasad AR.
Tetrahedron Lett.
2006,
47:
4995
4e </A>
Yadav JS.
Reddy MS.
Rao PP.
Prasad AR.
Synlett
2007,
2049
4f </A>
Yadav JS.
Rao PP.
Reddy MS.
Rao NV.
Prasad AR.
Tetrahedron Lett.
2007,
48:
1469
4g </A>
Yadav JS.
Kumar NN.
Reddy MS.
Prasad AR.
Tetrahedron
2006,
63:
2689
4h </A>
Rao AVR.
Reddy ER.
Joshi BV.
Yadav JS.
Tetrahedron
Lett.
1987,
28:
6497
4i </A>
Yadav JS.
Sridhar Reddy M.
Rao PP.
Prasad AR.
Synlett
2007,
2049
4j </A>
Yadav JS.
Hissana A.
Gayathri KU.
Rao NV.
Prasad AR.
Synthesis
2008,
3945
4k </A>
Yadav JS.
Thrimurtulu N.
Uma Gayathri K.
Reddy BVS.
Prasad AR.
Tetrahedron Lett.
2008,
49:
6617
5 </A>
Aldehyde 9 was
prepared from (R )-citronellol in two
steps in 76% overall yield as shown in Scheme
[4
Scheme 4
<A NAME="RD36109ST-6">6 </A>
Bouazza F.
Renoux B.
Bachmann C.
Gesson J.-P.
Org. Lett.
2003,
5:
4049
<A NAME="RD36109ST-7">7 </A>
Boger DL.
Yohannes D.
J. Org. Chem.
1988,
53:
487
<A NAME="RD36109ST-8">8 </A>
Inanaga J.
Hirata K.
Saeki H.
Katsuki T.
Yamaguchi M.
Bull.
Chem. Soc. Jpn.
1979,
52:
1989
9a </A>
Sakaitani M.
Ohfune Y.
J.
Org. Chem.
1990,
55:
870
9b </A>
Chandrasekhar S.
Yaragorla SR.
Sreelakshmi L.
Reddy ChR.
Tetrahedron
2008,
64:
5174
9c </A>
Chandrasekhar S.
Yaragorla SR.
Sreelakshmi L.
Tetrahedron
Lett.
2007,
48:
7339
10a </A>
Scholl M.
Ding S.
Lee C.
Grubbs RH.
Org.
Lett.
1999,
1:
953
10b </A>
Chatterjee AK.
Morgan JP.
Scholl M.
Grubbs RH.
J.
Am. Chem. Soc.
2000,
122:
3783
11 </A>
{(2
S
,4
R
)-6-[(
R
)-5-(Benzyloxy)-3-methylpentyl]-tetrahydro-4-(methoxymethoxy)-2
H
-pyran-2-yl} Methyl 4-Methylbenzenesulfonate (10)
9 (1.8 g, 3.78 mmol) in anhyd CH2 Cl2 (20
mL) at 0 ˚C were added DIPEA (1.31 mL, 7.56 mmol),
DMAP (cat.) and MOMCl (0.91 g, 11.34 mmol) successively, the resulting
mixture was stirred for 3 h at r.t. and then quenched by adding
H2 O (10 mL) and extracted with CH2 Cl2 (3 Ž 20
mL). The organic extracts were washed with brine (10 mL), dried
over anhyd Na2 SO4 , and concentrated under
reduced pressure to remove the solvent, and the crude residue was
purified by column chromatography to afford the pure product 10 as a liquid (1.80 g, 92%). R
f
= 0.7
(SiO2 , 10% EtOAc in hexane); clear oil; R
f
= 0.5
(EtOAc-hexane, 3:7). [α]D
²0 -2.6
(c 1.15, CHCl3 ). ¹ H
NMR (300 MHz, CDCl3 ): δ = 7.82-7.76
(m, 2 H), 7.38-7.22 (m, 7 H), 4.66 (s, 2 H), 4.49 (s, 2
H), 4.14-3.92 (m, 2 H), 3.73-3.61 (m, 1 H), 3.59-3.43
(m, 3 H), 3.35 (s, 3 H), 3.25-3.14 (m, 1 H), 2.43 (s, 3
H), 1.98-1.88 (dd, 2 H, J = 9.4,
2.8 Hz), 1.78-1.01 (m, 10 H), 0.87 (d, 3 H, J = 6.4 Hz). ¹³ C
NMR (75 MHz, CDCl3 ): δ = 144.6,
138.6, 132.9, 129.7, 128.3, 127.9, 127.5, 127.4, 94.3, 76.1, 72.8,
72.5, 72.4, 72.0, 68.5, 55.2, 38.0, 36.6, 34.4, 33.1, 32.5, 29.8,
21.5, 19.5. IR (KBr): νmax = 2922,
2852, 1456, 1362, 1037, 979 cm-¹ . ESI-MS: m/z = 521 [M+ + H],
543 [M+ + Na].(4
S
,6
S
,9
R
)-4-(Methoxymethoxy)-9-methyldodec-11-en-6-ol (16)
15 (0.8 g, 2.15 mmol) in anhyd THF (8 mL),
TBAF (4.3 mL, 4.3 mmol) was added, and the mixture was stirred at
0 ˚C for 2 h. The reaction mixture was quenched
with H2 O (5 mL) and extracted with EtOAc (2 × 5 mL),
and the combined organic layers washed with brine (10 mL), dried
over anhyd Na2 SO4 , and concentrated under reduced
pressure to remove the solvent. The crude residue was then purified
by column chromatography on silica gel (EtOAc-hexane, 1:9)
to afford 16 as a white solid; yield 0.46 g
(83%); clear oil; R
f
= 0.4
(EtOAc-hexane, 2:8); [α]D
²0 +12.1
(c 0.9, CHCl3 ). ¹ H
NMR (300 MHz, CDCl3 ): δ = 5.85-5.70
(m, 1 H), 5.05-4.94 (m, 2 H), 4.76-4.62 (m, 2 H),
3.90-3.76 (m, 2 H), 3.40 (s, 2 H), 2.13-2.02 (m,
1 H), 1.96-1.84 (m, 1 H), 1.68-1.08 (m, 10 H),
0.99-0.84 (m, 6 H). ¹³ C NMR
(75 MHz, CDCl3 ): δ = 137.5,
115.5, 96.2, 75.9, 68.2, 55.8, 41.2, 41.1, 37.0, 34.9, 32.9, 32.4,
19.4, 18.7, 14.1. IR (KBr): νmax = 3453,
2930, 1459, 1376, 1038, 911 cm-¹ . ESI-MS: m/z = 281 [M+ + Na].(2
S
)-(4
S
,6
S
,9
R
)-4-(Methoxymethoxy)-9-methyldodec-11-en-6-yl
3-{4-[2-(benzyloxy)ethoxy]phenyl}-2-(
N
-Methylbut-3-enamido)
Propanoate (19)
N -Boc-deprotected amine (200
mg, 0.35 mmol) in anhyd CH2 Cl2 (12 mL) was
added carboxylic acid fragment B (33 mg,
0.38 mmol) and then HOBt (4 mg, 0.035 mmol) followed by EDCI (201
mg, 1.05 mmol). The reaction was stirred for 6 h at r.t., quenched
with HCl (1 N, 15 mL), and diluted with Et2 O (20 mL).
The aqueous layer was extracted with Et2 O (20 mL), and
the resulting solution washed with brine (10 mL), dried over Na2 SO4 ,
filtered, and concentrated under reduced pressure. The residue was purified
by silica gel chromatography (EtOAc-hexane, 3:7) to afford
diene 2 as a colorless oil (160 mg, 75%). R
f
= 0.4 (EtOAc-hexane,
3:7); [α]D
²0 -9.3
(c 0.5,CHCl3 ). ¹ H
NMR (300 MHz, CDCl3 ): δ = 7.36-7.23
(m, 5 H), 7.11-7.01 (m, 2 H), 6.86-6.77 (m, 2
H), 5.85-5.65 (m, 2 H), 5.35-5.27 (m, 1 H), 5.11-4.90
(m, 4 H), 4.64-4.44 (m, 4 H), 4.13-4.06 (m, 2 H),
3.82-3.76 (m, 2 H), 3.51-3.39 (m, 1 H), 3.36-3.18
(m, 4 H), 3.14-2.86 (m, 4 H), 2.82 (s, 3 H), 2.10-1.96
(m, 1 H), 1.94-1.80 (m, 1 H), 1.67-1.19 (m, 11
H), 0.95-0.82 (m, 6 H). ¹³ C
NMR (75 MHz, CDCl3 ): δ = 171.1,
169.5, 157.6, 137.1, 131.0, 129.8, 129.1, 128.4, 127.7, 117.7, 115.9, 114.9,
114.6, 96.2, 74.5, 73.4, 72.8, 68.5, 67.3, 57.8, 55.8, 41.3, 39.2,
38.9, 37.4, 33.9, 32.7, 32.3, 31.6, 29.8, 19.4, 18.2, 14.3. IR (KBr): νmax = 2924,
2856, 1650, 1243, 1046 cm-¹ . ESI-MS: m/z = 660 [M+ + Na].(3
S
,10
R
,13
S
)-3-[4-(2-hydroxyethoxy)benzyl]-13-
S
-2-(methoxymethoxy)pentyl-4,10-dimethyl-1-oxa-4-azacyclotridecane-2,5-dione (21)
20 (0.200 g, 0.328 mmol) in EtOAc (10 mL)
was added Pd/C 10% (50 mg) and the mixture stirred
under H2 atmosphere for 7 h. After completion, the reaction
mass was filtered through Celite, and the solvent was removed under
reduced pressure to give crude product 21 .
Purification using column chromatog-raphy on silica gel (hexane-EtOAc,
4:1) gave pure product as a colorless solid (0.145 g, 85% yield); [α]D
²5 -48.5
(c 0.5, CHCl3 ). ¹ H
NMR (300 MHz, CDCl3 ): δ = 7.22-7.07
(m, 2 H), 6.83 (d, 2 H, J = 8.5
Hz), 5.13-5.02 (m, 1 H), 4.66-4.39 (m, 2 H), 4.08-4.02
(m, 2 H), 3.97-3.90 (m, 2 H), 3.35 (s, 3 H), 3.23-3.11
(t, 1 H, J = 11.1
Hz), 3.07-2.91 (m, 3 H), 2.88-2.57 (m, 1 H), 2.26-2.07
(m, 1 H), 1.72-1.08 (m, 19 H), 0.92-0.89 (m, 2
H), 0.85 (t, 3 H, J = 6.8
Hz), 0.81 (d, 3 H, J = 6.2
Hz). ¹³ C NMR (75 MHz, CDCl3 ): δ = 169.9, 130.2,
129.9, 114.8, 114.5, 75.4, 72.2, 69.0, 61.45, 55.7, 55.5, 39.0,
38.7, 37.3, 33.5, 33.3, 31.5, 30.1, 29.6, 25.1, 24.1, 20.5, 17.9,
14.2. IR (film): ν = 3437 (OH), 2926, 2869, 1728, 1636,
1512, 1247, 1038 cm-¹ . ESI-MS: m/z = 544 [M + Na]+ .(3
S
,10
R
,13
S
)-3-[4-(2-hydroxyethoxy)benzyl]-13-[(
S
)-2-hydroxy
pentyl]-4,10-dimethyl-1-oxa-4-azacyclotridecane-2,5-dione [PF1163
A (1)]
To a stirred
solution of 21 (0.02 g, 0.03 mmol) in anhyd TFA-CH2 Cl2 (1:5,
2 mL) was added at 0 ˚C, and the reaction mixture
was stirred for 2 h at r.t. The reaction mixture was quenched with
NaHCO3 (1 mL) and extracted with CH2 Cl2 (2 × 2
mL), and the combined organic layers were washed with brine (2 mL),
dried (Na2 SO4 ), and concentrated under reduced
pressure. The residue was purified by silica gel chromatography
(EtOAc-hexane, 3:7) to afford 1 as
a colorless oil (13 mg, 75%). R
f
= 0.4
(EtOAc-hexane, 7:3); [α]D
²0 -88.5
(c 1.0, MeOH). ¹ H
NMR (200 MHz, CDCl3 ): J = 7.8
Hz, 3 H), 0.82 (d, J = 7.8
Hz, 3 H). ¹³ C NMR (75 MHz, CDCl3 ): δ = 173.9, 171.7,
157.4, 130.3, 128.8, 114.5, 73.2, 69.1, 66.6, 61.3, 56.0, 49.4,
42.1, 39.0, 33.9, 33.2, 29.7, 24.1, 20.7, 19.0, 14.0. IR (KBr): νmax = 3429,
2924, 2856, 1728, 1632, 1511, 1459, 1247 cm-¹ .
ESI-HRMS: m/z [M + Na]+ calcd
for C27 H43 O6 NNa: 500.2988; found:
500.2979.
