Post on 01-Mar-2021
ESI-1
Electronic Supplementary Information
Effect of the allylic substituents on ring closing metathesis:The total synthesis of stagonolide B and 4-epi-stagonolide B
Awadut G. Giri, Mohabul A. Mondal, Vedavati G. Puranik and C. V. Ramana
Crystal Data for 2: Single crystals of the compound 2 were grown by slow evaporation a methanol solution of 2. Colourless crystal of approximate size 0.14 x 0.05 x 0.02 mm, was used for data collection on Bruker SMART APEX CCD diffractometer using Mo-Kα radiation with fine focus tube with 50kV and 30mA. All the data were corrected for Lorentzian, polarisation and absorption effects. SHELX-97 (ShelxTL) was used for structure solution and full matrix least squares refinement on F2. Hydrogen atoms were included in the refinement as per the riding model.
Table 1. Crystal data and structure refinement for 4-epi-stagonolide B.
Empirical formula C12H20O5 Formula weight 244.28 Temperature 295(2) K Wavelength 0.71073 A Crystal system, space group Monoclinic, C2 Unit cell dimensions a = 16.861(15) A alpha = 90 deg. b = 4.981(4) A beta = 112.087(14) deg. c = 16.109(14) A gamma = 90 deg. Volume 1253.7(19) A^3 Z, Calculated density 4, 1.294 Mg/m^3 Absorption coefficient 0.100 mm^-1 F(000) 528 Crystal size 0.14 x 0.05 x 0.02 mm Theta range for data collection 1.36 to 25.00 deg. Limiting indices -20<=h<=19, -5<=k<=5, -15<=l<=19 Reflections collected / unique 5114 / 2177 [R(int) = 0.1106] Completeness to theta = 25.00 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9979 and 0.9864 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 2177 / 1 / 158 Goodness-of-fit on F^2 0.835 Final R indices [I>2sigma(I)] R1 = 0.0720, wR2 = 0.1554 R indices (all data) R1 = 0.1490, wR2 = 0.1731 Absolute structure parameter 5(3) Largest diff. peak and hole 0.277 and -0.275 e.A^-3
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
ESI-2
Table 2. Atomic coordinates ( x 10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for 4-epi-stagonolide B. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. _______________________________________________________ x y z U(eq) ________________________________________________________________ O(1) 2588(2) 6950(8) 2109(3) 38(1) O(2) 2028(3) 11014(9) 2140(4) 60(2) O(3) 698(3) 7078(8) 4019(3) 44(1) O(4) 3724(3) 10129(8) 4195(3) 40(1) O(5) 4829(2) 7019(8) 3612(3) 42(1) C(1) 1940(4) 8615(16) 2048(4) 40(2) C(2) 1124(3) 7182(13) 1852(4) 39(2) C(3) 715(4) 7809(12) 2533(4) 42(2) C(4) 1188(4) 6654(13) 3467(4) 38(2) C(5) 2070(4) 7689(12) 3863(4) 38(2) C(6) 2751(4) 6297(11) 3892(4) 36(2) C(7) 3634(4) 7232(12) 4079(4) 39(2) C(8) 3928(3) 6572(12) 3335(4) 34(2) C(9) 3460(4) 7943(12) 2434(4) 37(2) C(10) 3813(4) 7322(14) 1735(4) 45(2) C(11) 3381(5) 8698(16) 844(4) 63(2) C(12) 3790(5) 8050(20) 172(5) 95(3) ________________________________________________________________ Table 3. Bond lengths [A] and angles [deg] for 4-epi-stagonolide B. _____________________________________________________________ O(1)-C(1) 1.346(8) O(1)-C(9) 1.450(7) O(2)-C(1) 1.207(8) O(3)-C(4) 1.439(6) O(3)-H(3') 0.8200 O(4)-C(7) 1.456(7) O(4)-H(4') 0.8200 O(5)-C(8) 1.431(6) O(5)-H(5') 0.8200 C(1)-C(2) 1.476(9) C(2)-C(3) 1.531(7) C(2)-H(2A) 0.9700 C(2)-H(2B) 0.9700 C(3)-C(4) 1.526(8) C(3)-H(3A) 0.9700
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
ESI-3
C(3)-H(3B) 0.9700 C(4)-C(5) 1.473(7) C(4)-H(4) 0.9800 C(5)-C(6) 1.328(7) C(5)-H(5) 0.9300 C(6)-C(7) 1.478(8) C(6)-H(6) 0.9300 C(7)-C(8) 1.496(8) C(7)-H(7) 0.9800 C(8)-C(9) 1.527(8) C(8)-H(8) 0.9800 C(9)-C(10) 1.490(8) C(9)-H(9) 0.9800 C(10)-C(11) 1.508(9) C(10)-H(10A) 0.9700 C(10)-H(10B) 0.9700 C(11)-C(12) 1.521(10) C(11)-H(11A) 0.9700 C(11)-H(11B) 0.9700 C(12)-H(12A) 0.9600 C(12)-H(12B) 0.9600 C(12)-H(12C) 0.9600 C(1)-O(1)-C(9) 120.1(5) C(4)-O(3)-H(3') 109.5 C(7)-O(4)-H(4') 109.5 C(8)-O(5)-H(5') 109.5 O(2)-C(1)-O(1) 122.8(6) O(2)-C(1)-C(2) 124.6(7) O(1)-C(1)-C(2) 112.6(6) C(1)-C(2)-C(3) 112.6(5) C(1)-C(2)-H(2A) 109.1 C(3)-C(2)-H(2A) 109.1 C(1)-C(2)-H(2B) 109.1 C(3)-C(2)-H(2B) 109.1 H(2A)-C(2)-H(2B) 107.8 C(4)-C(3)-C(2) 114.8(5) C(4)-C(3)-H(3A) 108.6 C(2)-C(3)-H(3A) 108.6 C(4)-C(3)-H(3B) 108.6 C(2)-C(3)-H(3B) 108.6 H(3A)-C(3)-H(3B) 107.5 O(3)-C(4)-C(5) 113.6(5) O(3)-C(4)-C(3) 110.2(5) C(5)-C(4)-C(3) 111.4(5)
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
ESI-4
O(3)-C(4)-H(4) 107.1 C(5)-C(4)-H(4) 107.1 C(3)-C(4)-H(4) 107.1 C(6)-C(5)-C(4) 123.4(5) C(6)-C(5)-H(5) 118.3 C(4)-C(5)-H(5) 118.3 C(5)-C(6)-C(7) 129.3(5) C(5)-C(6)-H(6) 115.3 C(7)-C(6)-H(6) 115.3 O(4)-C(7)-C(6) 112.8(5) O(4)-C(7)-C(8) 105.6(5) C(6)-C(7)-C(8) 112.2(5) O(4)-C(7)-H(7) 108.7 C(6)-C(7)-H(7) 108.7 C(8)-C(7)-H(7) 108.7 O(5)-C(8)-C(7) 110.4(5) O(5)-C(8)-C(9) 109.6(5) C(7)-C(8)-C(9) 117.1(5) O(5)-C(8)-H(8) 106.4 C(7)-C(8)-H(8) 106.4 C(9)-C(8)-H(8) 106.4 O(1)-C(9)-C(10) 107.1(5) O(1)-C(9)-C(8) 106.4(5) C(10)-C(9)-C(8) 114.5(5) O(1)-C(9)-H(9) 109.5 C(10)-C(9)-H(9) 109.5 C(8)-C(9)-H(9) 109.5 C(9)-C(10)-C(11) 116.0(5) C(9)-C(10)-H(10A) 108.3 C(11)-C(10)-H(10A) 108.3 C(9)-C(10)-H(10B) 108.3 C(11)-C(10)-H(10B) 108.3 H(10A)-C(10)-H(10B) 107.4 C(10)-C(11)-C(12) 113.3(6) C(10)-C(11)-H(11A) 108.9 C(12)-C(11)-H(11A) 108.9 C(10)-C(11)-H(11B) 108.9 C(12)-C(11)-H(11B) 108.9 H(11A)-C(11)-H(11B) 107.7 C(11)-C(12)-H(12A) 109.5 C(11)-C(12)-H(12B) 109.5 H(12A)-C(12)-H(12B) 109.5 C(11)-C(12)-H(12C) 109.5 H(12A)-C(12)-H(12C) 109.5 H(12B)-C(12)-H(12C) 109.5
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
ESI-5
_____________________________________________________________ Table 4. Anisotropic displacement parameters (A^2 x 10^3) for 4-epi-stagonolide B.. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ] _______________________________________________________________________ U11 U22 U33 U23 U13 U12 _______________________________________________________________________ O(1) 36(2) 27(2) 48(2) 1(2) 11(2) 8(2) O(2) 67(3) 17(3) 102(4) 6(3) 41(3) 9(2) O(3) 49(3) 32(3) 62(3) 8(3) 32(2) 5(3) O(4) 53(3) 26(2) 36(3) 0(2) 11(2) -6(2) O(5) 33(2) 29(2) 62(3) -6(3) 17(2) -1(2) C(1) 39(4) 50(5) 28(4) 10(4) 7(3) 0(4) C(2) 42(4) 30(4) 43(4) -13(4) 13(3) 6(4) C(3) 40(4) 28(4) 50(4) 1(3) 8(3) 0(3) C(4) 50(4) 27(4) 42(4) -4(3) 24(3) 4(3) C(5) 40(4) 30(4) 39(4) -4(3) 11(3) -1(3) C(6) 42(4) 15(3) 47(4) 5(3) 14(3) 4(3) C(7) 37(4) 29(4) 49(4) 8(4) 15(3) 5(3) C(8) 36(4) 20(3) 47(4) 3(3) 17(3) 4(3) C(9) 33(4) 28(4) 42(4) -4(3) 5(3) 2(3) C(10) 42(4) 47(5) 49(4) 4(4) 19(3) 7(4) C(11) 82(6) 61(5) 45(4) 7(4) 23(4) -4(4) C(12) 100(7) 142(10) 57(5) 13(6) 47(5) -6(6) _______________________________________________________________________ Table 5. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for 4-epi-stagonolide B.. ________________________________________________________________ x y z U(eq) ________________________________________________________________ H(3') 616 8690 4052 66 H(4') 3913 10492 4730 60 H(5') 4937 8599 3752 62 H(2A) 1224 5265 1852 47 H(2B) 728 7678 1259 47 H(3A) 681 9743 2583 50
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
ESI-6
H(3B) 134 7117 2306 50 H(4) 1228 4709 3399 45 H(5) 2154 9408 4107 45 H(6) 2660 4470 3777 43 H(7) 4019 6363 4629 46 H(8) 3839 4639 3228 40 H(9) 3460 9890 2521 44 H(10A) 3778 5398 1636 54 H(10B) 4414 7808 1967 54 H(11A) 3400 10624 939 75 H(11B) 2784 8163 595 75 H(12A) 4402 8082 468 142 H(12B) 3616 9361 -299 142 H(12C) 3611 6299 -76 142 ________________________________________________________________ Table 6. Torsion angles [deg] for 4-epi-stagonolide B.. ________________________________________________________________ C(9)-O(1)-C(1)-O(2) 10.0(9) C(9)-O(1)-C(1)-C(2) -170.3(5) O(2)-C(1)-C(2)-C(3) -54.6(9) O(1)-C(1)-C(2)-C(3) 125.7(6) C(1)-C(2)-C(3)-C(4) -69.8(8) C(2)-C(3)-C(4)-O(3) -173.0(5) C(2)-C(3)-C(4)-C(5) 59.9(7) O(3)-C(4)-C(5)-C(6) 133.4(6) C(3)-C(4)-C(5)-C(6) -101.5(7) C(4)-C(5)-C(6)-C(7) 165.2(6) C(5)-C(6)-C(7)-O(4) -3.9(9) C(5)-C(6)-C(7)-C(8) -123.0(7) O(4)-C(7)-C(8)-O(5) 68.2(6) C(6)-C(7)-C(8)-O(5) -168.6(5) O(4)-C(7)-C(8)-C(9) -58.1(6) C(6)-C(7)-C(8)-C(9) 65.1(7) C(1)-O(1)-C(9)-C(10) -124.5(5) C(1)-O(1)-C(9)-C(8) 112.5(5) O(5)-C(8)-C(9)-O(1) 168.2(4) C(7)-C(8)-C(9)-O(1) -65.0(6) O(5)-C(8)-C(9)-C(10) 50.1(7) C(7)-C(8)-C(9)-C(10) 176.8(5) O(1)-C(9)-C(10)-C(11) 63.8(7) C(8)-C(9)-C(10)-C(11) -178.5(5) C(9)-C(10)-C(11)-C(12) 178.1(6) ________________________________________________________________
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
4 Au
g 20
09
Acq
uisi
tion
Tim
e (s
ec)
3.98
46D
ate
04/0
5/20
09 1
7:41
:22
Freq
uenc
y (M
Hz)
400.
13N
ucle
us1H
Orig
inal
Poi
nts
Cou
nt32
768
Poin
ts C
ount
3276
8Sw
eep
Wid
th (H
z)82
23.6
8Te
mpe
ratu
re (g
rad
C)
0.00
0
Chl
orof
orm
-d
0.880.921.231.301.321.421.521.611.821.922.032.102.152.232.252.422.49
3.553.59
4.504.61
4.914.96
5.615.66
5.976.01
7.25
ES
I-7
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
3.00
1.89
1.73
1.11
1.02
0.91
0.90
0.88
0.86
0.86
0.76
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
4 Au
g 20
09
Acq
uisi
tion
Tim
e (s
ec)
1.36
31D
ate
22/0
4/20
09 1
2:15
:12
Freq
uenc
y (M
Hz)
100.
61N
ucle
us13
CO
rigin
al P
oint
s C
ount
3276
8Po
ints
Cou
nt32
768
Swee
p W
idth
(Hz)
2403
8.46
Tem
pera
ture
(gra
d C
)0.
000
Chl
orof
orm
-d
3.84
7.97
7.781.603.59
8.550.223.577.00
27.1527.22
76.48
13
17
273133
68707377
1212
17
ES
I-8
200
190
180
170
160
150
140
130
120
110
100
9080
7060
5040
3020
100
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
4 A
ug 2
009
Acq
uisi
tion
Tim
e (s
ec)
1.36
31D
ate
22/0
4/20
09 1
1:41
:52
Freq
uenc
y (M
Hz)
100.
61N
ucle
us13
CO
rigin
al P
oint
s C
ount
3276
8Po
ints
Cou
nt32
768
Swee
p W
idth
(Hz)
2403
8.46
Tem
pera
ture
(gra
d C
)0.
000
13.84
17.97
27.78
31.5933.58
68.5470.2173.60
127.14
ES
I-9
190
180
170
160
150
140
130
120
110
100
9080
7060
5040
3020
100
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
fdfsd
aM
A MO
NDAL
Acqu
isitio
n Tim
e (se
c)3.6
351
Comm
ent
M A
MOND
ALDa
te31
/05/20
08 0
3:06:4
6Fr
eque
ncy (
MHz)
500.1
3Nu
cleus
1HOr
igina
l Poin
ts Co
unt
3276
8Po
ints C
ount
3276
8Sw
eep W
idth (
Hz)
9014
.42Te
mper
ature
(gra
d C)
0.000
OH
0.900.910.931.241.291.381.431.511.761.851.891.942.012.072.252.29
3.313.313.493.52
4.034.11
4.384.39
4.915.115.165.475.52
5.755.79
OO
H
OH
O
ES
I-10
4-ep
i-Sta
gono
lide
B( e
pi- 2
)
10.0
9.59.0
8.58.0
7.57.0
6.56.0
5.55.0
4.54.0
3.53.0
2.52.0
1.51.0
0.50.0
5.15
3.33
1.97
1.18
1.04
1.04
1.00
0.93
0.93
0.93
0.75
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
OH
Acqu
isiti
on T
ime
(sec
)1.
0486
Date
27/0
5/20
08 1
4:07
:16
Freq
uenc
y (M
Hz)
125.
76Nu
cleu
s13
CO
rigin
al P
oint
s Co
unt
3276
8Po
ints
Cou
nt32
768
Swee
p W
idth
(Hz)
3125
0.00
Tem
pera
ture
(gra
d C)
0.00
0
OO
H
OH
OE
SI-1
1
49.10
O
4-ep
i-Sta
gono
lide
B( e
pi- 2
)
14.44
18.92
32.5433.93
35.06
71.8773.634.645.90
28.16
33.48
3
7747
1
13
176.27
180
170
160
150
140
130
120
110
100
9080
7060
5040
3020
100
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
4 A
ug 2
009
Acq
uisi
tion
Tim
e (s
ec)
1.10
10D
ate
27/0
5/20
08 1
3:19
:02
Freq
uenc
y (M
Hz)
125.
76N
ucle
us13
CO
rigin
al P
oint
s C
ount
3276
8Po
ints
Cou
nt32
768
Swee
p W
idth
(Hz)
2976
1.90
Tem
pera
ture
(gra
d C
)0.
000
14.16
18.64
32.2633.6434.78
49.10
71.5773.3374.3475.61
127.86
133.21
OH
OO
H
OH
OH
ES
I-12
O
4-ep
i-Sta
gono
lide
B( e
pi- 2
)
190
180
170
160
150
140
130
120
110
100
9080
7060
5040
3020
10
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009
5.225.235.29
5.29
Det
erm
inat
ion
of th
e ab
solu
te s
tere
oche
mis
try o
f alc
ohol
(R)-
10
ES
I-12
5.175.205.21
5.225
5.30 5.315.39
5.395.40
5.455.48
5.51
5.635.67
5.685.72
5.755.77
5.805.82
571
1.40
1.446
1.50511.531.531.55
1.571.58
1.651.69
1.701.71
1.741.77
1.80
(S)-
Mos
cher
Est
er
5.85.85.91
1.36
1.42
1.4
11.
1
1.811.83
235.23
5.285.285.29
5.315.395.39 0
0
4
5.82
1.56
.69
5.225.2
5
5.31
5.45.43
5.455.475.50
5.53
5.745.775.79
5.865.87
5.91
1.391.40
1.421.44
1.471.47
1.501.50
1.66
1 1.701.721.721.74
1.761.77
(R)-
Mos
cher
Est
er
12
34
5
(S)-
MT
PA5.
235.
721.
761.
493.
57
(R)-
MT
PA5.
315.
821.
711.
413.
54(R
)M
TPA
5.31
5.82
1.71
1.41
3.54
Δδ=
(Sδ–δR
) x 1
000
-80
-100
+50
+80
+30
-Δδ
+Δδ
Supplementary Material (ESI) for Organic and Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2009