Effect of the allylic substituents on ring closing metathesis:The … · 2009. 10. 20. · ESI-1...

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


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)


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


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


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) ________________________________________________________________


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Effect of the allylic substituents on ring closing metathesis:The … · 2009. 10. 20. · ESI-1...

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Transcript of Effect of the allylic substituents on ring closing metathesis:The … · 2009. 10. 20. · ESI-1...