Jogireddy and Maier
3.47-3.51 (m, 1H, CHCOPh), 3.52 (s, 3H, OCH2OCH3), 3.60 (ddd,
J ) 11.8, 10.0, 6.7 Hz, 1H, CH2OH), 3.76 (dd, J ) 9.9, 6.3 Hz,
0.5H, CHCquatepoxide), 3.82 (dd, J ) 11.9, 5.1 Hz, 0.5H, CH2-
purification and separation should be done on diol-modified silica
gel (Merck 40-63 µm, 2% MeOH/CH2Cl2). The NMR spectra (1H,
13C) data matched the reported ones. The epi-compound turned out
to be a mixture (1:1) of anomers.
OH), 3.91-3.98 (m, 1H, (0.5H) CH2OH and (0.5H) CHCquat
epoxide), 4.02-4.09 (m, 1H, CHCHCOPh), 5.01 (s, 4H, OCH2-
OCH3), 7.52 (s, 1H, CHortho), 10.25, 10.26 (s, 1H, CHO) ppm. 13
-
Luminacin D (1): First Spot. Rf ) 0.27 (silica gel, 30%
C
acetone/hexane); 0.2 (diol-modified silica gel, 2% MeOH/DCM);
NMR (100 MHz, CDCl3): δ ) 10.6, 10.7 (CH3CH2), 14.4 (CH3-
CH2CH2), 20.1, 20.2 (CH2CH2CH), 21.2 (CH2CH3), 22.3, 22.4
((CH3)2CH), 24.3, 24.4 ((CH3)2C), 24.4, 24.6 ((CH3)2C), 28.8 (CH-
[R]20 ) -12.2 (c 0.2 in CHCl3). IR (film): νmax ) 3446, 2958,
D
2930, 2853, 1735, 1693, 1461, 1384, 1253, 1199, 1133, 1075, 1039,
763 cm-1. 1H NMR (600 MHz, CDCl3): δ ) 0.88 (t, J ) 7.5 Hz,
3H, 11′-CH2CH3), 0.89 (d, J ) 6.6 Hz, 3H, (CH3)2CH), 0.90 (d, J
) 6.4 Hz, 3H, (CH3)2CH), 0.92 (t, J ) 7.6 Hz, 3H, 10′-H), 1.19-
1.30 (m, 1H, 11′-CH2CH3), 1.37-1.47 (m, 2H, 11′-CH2CH3, 9-H′),
1.50 (q, J ) 12.1 Hz, 1H, 4′-H), 1.63-1.71 (m, 2H, 9′-H, 11′-H),
1.83-1.91 (m, 2H, 11′-H, (CH3)2CH), 2.12 (ddd, J ) 12.7, 4.5,
1.9 Hz, 1H, 4′-H), 2.41 (dd, J ) 13.9, 7.6 Hz, 1H, CH2iPr), 2.45
(dd, J ) 13.9, 7.6 Hz, 1H, CH2iPr), 2.81 (br s, 1H, OH), 3.27 (t,
J ) 6.7 Hz, 1H, 8′-H), 3.54-3.58 (m, 1H, 2′-H), 4.38 (dd, J )
11.4, 5.1 Hz, 1H, 5′-H), 4.45 (ddd, J ) 11, 7.6, 1.5 Hz, 1H, 3′-H),
4.96 (s, 1H, 7′-H), 7.73 (s, 1H, 4-H), 10.39 (s, 1H, CHO), 12.97
(s, 1H, 6-OH), 14.15 (s, 1H, 2-OH) ppm. 13C NMR (150 MHz,
CDCl3): δ ) 10.0 (C-10′), 14.2 (11′-CH2CH3), 20.7 (11′-CH2CH3),
21.2 (C-9′), 22.2 ((CH3)2CH), 28.2 ((CH3)2CH), 31.7 (C-11′), 36.5
(C-4′), 37.9 (CH2iPr), 49.0 (C-2′), 59.2 (C-8′), 62.8 (C-5′), 64.3
(C-6′), 69.8 (C-3′), 92.5 (C-7′), 109.2 (C-1), 112.5 (C-3), 120.8
(C-5), 139.7 (C-4), 167.4 (2), 167.9 (C-6), 194.3 (CHO), 206.5
(C-1′) ppm. HRMS (ESI): calcd for C24H34O8Na [M + Na]+,
473.2146; found, 473.2143.
(CH3)2), 29.9, 30.1 (CH2CHCOPh), 30.3, 30.8 (CH2CHCquat
-
epoxide), 39.1 (CH2CH(CH3)2), 54.3 (CHCOPh), 57.7, 58.2
(OCH2OCH3), 60.7, 60.8 (CH2OH), 61.5, 61.9 (CH epoxide), 62.3,
62.9 (Cquatepoxide), 67.2, 67.3 (CHCHCOPh), 68.4, 70.6 (CHCquat
-
epoxide), 101.0, 101.1 (C(CH3)2), 102.2, 103.1 (OCH2OCH3), 124.1
(Cquat), 130.7, 130.8 (Cquat), 132.3, 132.4 (Cquat), 136.7 (CHortho),
157.0, 157.1 (Cquat), 159.7, 159.8 (Cquat), 189.8, 189.9 (CHO), 203.3,
203.4 (CdO) ppm. HRMS (ESI): calcd for C31H48O10Na [M +
Na]+, 603.3140; found, 603.3142.
3-Ethyl-2-((4R,6R)-6-{(1S)-1-[3-formyl-5-isobutyl-2,4-bis-
(methoxymethoxy)benzoyl]butyl}-2,2-dimethyl-1,3-dioxan-4-yl)-
oxirane-2-carbaldehyde (44). To a stirred solution of the foregoing
epoxy alcohols 43 (24 mg, 0.041 mmol) in CH2Cl2 (1.5 mL) was
added Dess-Martin periodinane (26.3 mg, 0.062 mmol) in CH2-
Cl2 (0.4 mL) dropwise at room temperature. After stirring at room
temperature for 45 min, the reaction was quenched with 10%
aqueous Na2S2O3 solution (1 mL) and diluted with ether (2 mL).
The layers were separated and the aqueous layer was extracted with
ether (3 × 1 mL). The combined organic layers were washed with
saturated aqueous NaHCO3 (2 mL) and brine (2 mL), dried over
MgSO4, filtered and concentrated in vacuo. The crude product was
filtered through a short pad of silica gel to obtain the dialdehydes
44 (22 mg, 93%) as a slightly yellow oil. Rf ) 0.31 (25% EtOAc/
petroleum ether). IR (film): νmax ) 2958, 2938, 2873, 1693, 1569,
6′,8′-epi-Luminacin (6′,8′-epi-1): Second Spot. Rf ) 0.20 (silica
gel, 30% acetone/hexane); 0.31 (diol-modified silica gel, 4%
MeOH/CH2Cl2); [R]20 ) +6.3 (c 0.3 in CHCl3). IR (film): νmax
D
) 3450, 2958, 2873, 1633, 1461, 1384, 1253, 1199, 1133, 1075,
1
1039, 763 cm-1. H NMR (600 MHz, CDCl3): δ ) 0.85 (t, J )
1
1461, 1384, 1253, 1199, 1172, 1133, 763 cm-1. H NMR (400
7.6 Hz, 3H, 11′-CH2CH3), 0.88 (d, J ) 6.7 Hz, 1.5H, (CH3)2CH),
0.89 (d, J ) 6.7 Hz, 1.5H, (CH3)2CH), 0.90 (d, J ) 7.0 Hz, 3H,
(CH3)2CH), 1.05 (t, J ) 7.3 Hz, 1.5H, 10′-H), 1.09 (t, J ) 7.3 Hz,
1.5H, 10′-H), 1.16-1.27 (m, 2H, 11′-CH2CH3), 1.35-1.64 (m, 2H,
9′-H), 1.67 (dd, J ) 12.1, 4.5 Hz, 1H, 4′-H), 1.75-1.82 (m, 2H,
4′-H, 11′-H), 1.86-1.96 (m, 2H, 11′-H, (CH3)2CH), 2.33-2.38 (m,
1H, CH2iPr), 2.43-2.50 (m, 1H, CH2iPr), 3.56-3.59 (m, 2H, 3′-
H, 2′-H), 3.60-3.64 (m, 0.5H, 8′-H), 3.98 (dd, J ) 11.4, 5 Hz,
0.5H, 5′-H), 4.23-4.27 (m, 0.5H, 8′-H), 4.35 (dd, J ) 11.4, 5 Hz,
0.5H, 5′-H), 4.53 (s, 0.5H, 7′-H), 5.13 (s, 0.5H, 7′-H), 7.73 (s, 0.5H,
4-H), 7.74 (s, 0.5H, 4-H), 10.39 (s, 1H, CHO), 12.97 (s, 0.5H,
6-OH), 12.98 (s, 0.5H, 6-OH), 14.09 (s, 0.5H, 2-OH), 14.15 (s,
0.5H, 2-OH) ppm. 13C NMR (150 MHz, CDCl3): δ ) 11.1, 11.3
(C-10′), 14.2 (11′-CH2CH3), 20.4, 20.5 (11′-CH2CH3), 22.2, 22.4
((CH3)2CH), 23.6, 25.1 (C-9′), 28.2 ((CH3)2CH), 32.2, 32.5 (C-
11′), 32.9, 33.3 (C-4′), 37.9 (CH2iPr), 49.3, 49.6 (C-2′), 64.6 (C-
5′), 69.2, 69.5 (C-8′), 72.0, 72.5 (C-3′), 74.3, 74.5 (C-6′), 94.6,
95.8 (C-7′), 109.3 (C-1), 112.4, 112.5 (C-3), 121.1, 121.3 (C-5),
139.3, 139.4 (C-4), 167.4 (C-2), 168.0, 168.1 (C-6), 194.2, 194.3
(CHO), 206.7, 207.0 (C-1′) ppm. HRMS (ESI): calcd for C24H34O8-
Na + H2O [M + Na]+, 491.2251; found, 491.2254.
MHz, CDCl3): δ ) 0.80 (t, J ) 7.3 Hz, 3H, CH3CH2CH2), 0.82-
0.91 (m, 6H, (CH3)2CH), 1.01 (t, J ) 7.5 Hz, 1.5H, CH3CH2), 1.04
(t, J ) 7.5 Hz, 1.5H, CH3CH2), 1.24 (s, 6H, (CH3)2C), 1.28-2.00
(m, 9H, (2H) CH2CH2CH, (2H) CH2CH3, (1H) CH(CH3)2, (2H)
CH2CHCquatepoxide and (2H) CH2CHCOPh), 2.53 (d, J ) 7.1 Hz,
1H, CH2CH(CH3)2), 2.54 (d, J ) 7.1 Hz, 1H, CH2CH(CH3)2), 2.98
(dd, J ) 7.1, 5.8 Hz, 0.5H, CHepoxide), 3.36 (dd, J ) 7.5, 5.8 Hz,
0.5H, CHepoxide), 3.46 (s, 3H, OCH2OCH3), 3.51-3.55 (m, 1H,
CHCOPh), 3.57 (s, 3H, OCH2OCH3), 4.02-4.07 (m, 1H, CHCquat
-
epoxide), 4.28 (dd, J ) 9.8, 6.3 Hz, 0.5H, CHCHCOPh), 4.52 (dd,
J ) 9.8, 6.6 Hz, 0.5H, CHCHCOPh), 5.05, 5.06 (s, 2H, OCH2-
OCH3), 7.56 (d, J ) 5.6 Hz, 1H, CHortho), 9.42 (s, 0.5H, CHO),
9.51 (s, 0.5H, CHO), 10.30, 10.31 (CHO) ppm. 13C NMR (100
MHz, CDCl3): δ ) 10.5, 10.7 (CH3CH2), 14.3 (CH3CH2CH2), 20.2,
20.3 (CH2CH3), 21.2, 21.3 (CH2CH2CH), 22.3, 22.4 ((CH3)2CH),
23.8, 24.1 ((CH3)2C), 24.3, 24.5 ((CH3)2C), 28.8 (CH(CH3)2), 29.0
(CH2CHCOPh), 30.0, 30.2 (CH2CHCquatepoxide), 39.1 (CH2CH-
(CH3)2), 54.1, 54.2 (CHCOPh), 57.6, 57.7 (OCH2OCH3), 58.1, 58.2
(OCH2OCH3), 62.8 (CHepoxide), 63.8, 64.2 (CHCHCOPh), 66.2,
67.0 (Cquatepoxide), 67.1, 67.2 (CHCquatepoxide), 100.9, 101.1
((C(CH3)2), 102.2, 103.1 (OCH2OCH3), 124.0 (Cquat), 130.7, 130.8
(Cquat), 132.3 (Cquat), 136.7, 136.8 (CHortho), 157.1, 157.2 (Cquat),
159.6, 159.7 (Cquat), 189.8, 189.9 (CHO), 199.3, 199.4 (CHO),
203.2, 203.4 (CdO) ppm. HRMS (ESI): calcd for C31H46O10Na
[M + Na]+, 601.2983; found, 601.2990.
Luminacin D (1) and 6′,8′-epi-Luminacin (6′,8′-epi-1). A
mixture of acetal 44 (21 mg, 0.036 mmol), THF (0.38 mL), AcOH
(0.38 mL) and water (0.2 mL) was stirred for 3 h at 95 °C. After
cooling, the mixture was concentrated in vacuo. The residue was
diluted with toluene, and the solvent removed in vacuo. This was
repeated several times to remove the acetic acid. The crude product
was purified by flash chromatography (50% EtOAc/petroleum ether)
to furnish pure luminacin D (1) (8 mg, 49%) and the epoxide
diastereomer 6′,8′-epi-1 (5 mg, 31%) as colorless oils: Rf ) 0.30
(50% EtOAc/petroleum ether). To avoid decomposition, further
Acknowledgment. Financial support by the Deutsche For-
schungsgemeinschaft (Grant Ma 1012/16-1) and the Fonds der
Chemischen Industrie is gratefully acknowledged. In addition,
we acknowledge partial support by COST D28. We also thank
Degussa for a gift of amino acids.
Supporting Information Available: Experimental procedures
and characterization for all other new compounds reported and
copies of NMR spectra for important intermediates. This material
JO061104G
7006 J. Org. Chem., Vol. 71, No. 18, 2006