Remote Asymmetric Induction in an Intramolecular Ionic Diels-Alder Reaction: Application to the Total Synthesis of (+)-Dihydrocompactin

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1 Page S16 Remote Asymmetric Induction in an Intramolecular Ionic Diels-Alder Reaction: Application to the Total Synthesis of (+)-Dihydrocompactin Tarek Sammakia,* Deidre M. Johns, Ganghyeok Kim, and Martin A. Berliner Department of Chemistry and Biochemistry University of Colorado, Boulder, Colorado Supporting Information- X-ray crystallography data for ent-11 Table 1. Crystal data for C 16 H 26 O 3. Identification code bc426 Empirical formula C 16 H 26 O 3 Formula mass Crystal size, mm Crystal color, habit colorless parallelepiped Crystal system monoclinic Space group P2 1 a, Å 5.521(3) b, Å 7.874(4) c, Å (8) α, 90 β, 96.83(4) γ, 90 Volume, Å (7) Z, formula units/cell 2 Density (calculated), Mg m Absorption coefficient, mm F(000) 292 Absorption correction none Range Transmission Coefficients and

2 Page S17 Table 2. Data collection parameters for C 16 H 26 O 3. Diffractometer Siemens SMART CCD area detector Temperature, K 143(2) Radiation source sealed tube Wavelength, Å MoKα Monochromator graphite Cell measurement Reflections used 1607 θ range < θ < θ range, data collection 1.14 < θ < Scan type ω scans Index ranges -7 h 7, -10 k 8, 0 l 23 Reflections collected 7622 Independent reflections 2760 (R(int)= ) Standard reflections 50 frames re-measured Stability of standards no decay observed

3 Page S18 Table 3. Structure Solution and Refinement for C 16 H 26 O 3. System used 1,2 SHELXS-97 (Sheldrick, 1990) Structure solution direct Data/ restraints/ parameters 2760 / 1/ 172 Hydrogen atoms riding, with riding isotropic U weighting scheme calc w -1 =[σ 2 2 ( )+(0.0727P) 2 ] where F o F c F o 2 2 P=( +2 ) 3 Final R indices 3 [I>2σ(I)] R1 = , wr2 = Reflections observed 1842 R indices (all data) R1 = , wr2 = Goodness-of-fit 4 on F Absolute structure parameter 5 0(2) Largest diff. peak and hole and ) G. M. Sheldrick, SHELXTL, A Program for Crystal Structure Determination. Version 5.03, 1995, Siemens Analytical X-ray Instruments, Madison, Wisconsin. 2) Scattering factors (neutral atoms) are from "International Tables for Crystallography" Vol. C, D. Reidel Publishing Co. Boston, ) R1 = F o F F o c ; wr2 = 2 w(f F ) o w(f ) 2 2 c 2 2 o ; wf ( F) o c 4) GooF = S = where M is the number of reflections and N is the ( M N) number of parameters refined. 5) H. D. Flack, Acta Cryst. 1983, A39,

4 Page S19 Table 4. Atomic coordinates and equivalent isotropic displacement parameters (Å 2 ) for C 16 H 26 O 3. U eq is defined as one-third of the trace of the orthogonalized U ij tensor. x y z Ueq O(1) (4) (3) (11) (5) O(2) (3) (3) (9) (5) O(3) (3) (3) (11) (5) C(1) (5) (4) (14) (6) C(2) (5) (4) (15) (7) C(3) (6) (4) (17) (8) C(4) (6) (5) (16) (8) C(5) (6) (5) (16) (8) C(6) (5) (4) (15) (7) C(7) (6) (4) (17) (8) C(8) (6) (5) (18) (8) C(9) (6) (4) (16) (7) C(10) (5) (4) (14) (6) C(11) (6) (5) (17) (9) C(12) (5) (4) (16) (7) C(13) (5) (4) (16) (7) C(14) (5) (4) (15) (7) C(15) (5) (4) (15) (7) C(16) (5) (5) (15) (7)

5 Page S20 Table 5. Bond lengths (Å) for C 16 H 26 O 3. O(1)-C(2) 1.219(4) O(2)-C(14) 1.439(3) O(3)-C(16) 1.428(3) C(1)-C(2) 1.517(4) C(1)-C(10) 1.529(4) C(1)-C(6) 1.547(4) C(2)-C(3) 1.499(4) C(3)-C(4) 1.536(5) C(4)-C(5) 1.523(5) C(5)-C(6) 1.536(4) C(6)-C(7) 1.499(4) C(7)-C(8) 1.330(4) C(8)-C(9) 1.486(5) C(9)-C(11) 1.540(4) C(9)-C(10) 1.551(4) C(10)-C(12) 1.543(4) C(12)-C(13) 1.534(4) C(13)-C(14) 1.525(4) C(14)-C(15) 1.512(4) C(15)-C(16) 1.512(4) Table 6. Bond angles ( ) for C 16 H 26 O 3. C(2)-C(1)-C(10) 115.7(3) C(2)-C(1)-C(6) 103.5(2) C(10)-C(1)-C(6) 112.3(2) O(1)-C(2)-C(3) 122.8(3) O(1)-C(2)-C(1) 122.5(3) C(3)-C(2)-C(1) 114.3(3) C(2)-C(3)-C(4) 109.7(3) C(5)-C(4)-C(3) 112.8(2) C(4)-C(5)-C(6) 111.2(3) C(7)-C(6)-C(5) 113.3(3) C(7)-C(6)-C(1) 111.4(2) C(5)-C(6)-C(1) 109.8(2) C(8)-C(7)-C(6) 122.6(3) C(7)-C(8)-C(9) 126.2(3) C(8)-C(9)-C(11) 108.9(3) C(8)-C(9)-C(10) 111.5(2) C(11)-C(9)-C(10) 115.2(3) C(1)-C(10)-C(12) 112.1(2) C(1)-C(10)-C(9) 111.0(3) C(12)-C(10)-C(9) 112.4(2) C(13)-C(12)-C(10) 113.1(2) C(14)-C(13)-C(12) 114.4(2) O(2)-C(14)-C(15) 110.6(2) O(2)-C(14)-C(13) 108.0(2) C(15)-C(14)-C(13) 110.2(2) C(14)-C(15)-C(16) 115.0(2) O(3)-C(16)-C(15) 108.3(2)

6 Page S21 Table 7. Anisotropic displacement parameters (Å 2 ) for C 16 H 26 O 3. The anisotropic displacement factor exponent takes the form: -2π 2 [(ha*) 2 U hka*b*U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 O(1) (11) (13) (11) (11) (9) (12) O(2) (10) (12) (10) (9) (8) (10) O(3) (11) (13) (12) (12) (9) (12) C(1) (14) (15) (12) (14) (10) (15) C(2) (16) (19) (16) (13) (13) (14) C(3) (17) 0.033(2) (16) (14) (14) (16) C(4) (18) 0.045(2) (15) (18) (13) (2) C(5) (18) 0.038(2) (16) (15) (14) (16) C(6) (16) (18) (15) (14) (12) (14) C(7) (19) (18) (18) (15) (15) (16) C(8) 0.054(2) (17) (19) (16) (16) (17) C(9) (18) (19) (15) (15) (13) (16) C(10) (14) (15) (13) (14) (11) (15) C(11) 0.059(2) 0.044(2) (17) (16) (16) (18) C(12) (16) (18) (15) (14) (12) (15) C(13) (16) (18) (15) (14) (12) (15) C(14) (15) (18) (13) (12) (11) (13) C(15) (15) (18) (14) (13) (12) (14) C(16) (14) (18) (14) (16) (12) (16)

7 Page S22 Table 8. Hydrogen coordinates and isotropic displacement parameters (Å 2 ) for C 16 H 26 O 3. x y z Ueq H(2A) H(3A) H(1A) H(3B) H(3C) H(4A) H(4B) H(5A) H(5B) H(6A) H(7A) H(8A) H(9A) H(10A) H(11A) H(11B) H(11C) H(12A) H(12B) H(13A) H(13B) H(14A) H(15A) H(15B) H(16A) H(16B) Table 9. Hydrogen bonded atoms (Å 2 ) for C 16 H 26 O 3. donor acceptor D-H bond H-A distance D-A distance D-H-A angle required symmetry operation O(2)-H(2A) O(3) (3) x-1, y-1/2, -z+1 O(3)-H(3A) O(2) (3) x-1, y, z

8 Page S23 Table 10. Torsion angles for C 16 H 26 O 3. C(10)-C(1)-C(2)-O(1) -14.9(4) C(7)-C(8)-C(9)-C(10) 13.4(5) C(6)-C(1)-C(2)-O(1) 108.4(3) C(2)-C(1)-C(10)-C(12) -56.6(3) C(10)-C(1)-C(2)-C(3) 171.7(2) C(6)-C(1)-C(10)-C(12) (2) C(6)-C(1)-C(2)-C(3) -65.1(3) C(2)-C(1)-C(10)-C(9) 176.8(2) O1)-C(2)-C(3)-C(4) (3) C(6)-C(1)-C(10)-C(9) 58.3(3) C(1)-C(2)-C(3)-C(4) 58.0(3) C(8)-C(9)-C(10)-C(1) -41.2(3) C(2)-C(3)-C(4)-C(5) -48.0(3) C(11)-C(9)-C(10)-C(1) 83.6(3) C(3)-C(4)-C(5)-C(6) 50.5(3) C(8)-C(9)-C(10)-C(12) (3) C(4)-C(5)-C(6)-C(7) 175.1(2) C(11)-C(9)-C(10)-C(12) -42.8(3) C(4)-C(5)-C(6)-C(1) -59.6(3) C(1)-C(10)-C(12)-C(13) 166.1(2) C(2)-C(1)-C(6)-C(7) (2) C(9)-C(10)-C(12)-C(13) -68.1(3) C(10)-C(1)-C(6)-C(7) -44.4(3) C(10)-C(12)-C(13)-C(14) 170.4(2) C(2)-C(1)-C(6)-C(5) 63.7(3) C(12)-C(13)-C(14)-O(2) -68.2(3) C(10)-C(1)-C(6)-C(5) (2) C(12)-C(13)-C(14)-C(15) 170.9(3) C(5)-C(6)-C(7)-C(8) 140.3(3) O(2)-C(14)-C(15)-C(16) 58.6(3) C(1)-C(6)-C(7)-C(8) 15.9(4) C(13)-C(14)-C(15)-C(16) 178.0(3) C(6)-C(7)-C(8)-C(9) -0.6(5) C(14)-C(15)-C(16)-O(3) (2) C(7)-C(8)-C(9)-C(11) (4)

9 Page S24 Notes on the structure determination for C 16 H 26 O 3. Crystals were examined under a light hydrocarbon oil and mounted with silicone vacuum grease to a thin glass fiber affixed to a tapered copper mounting-pin. This assembly was transferred to the goniometer of a Siemens SMART CCD diffractometer equipped with a locally modified LT- 2A low-temperature apparatus operating at 143 K. Three crystals were examined and abandoned for weak diffraction and other defects before locating the specimen crystal. While also exhibiting weak diffraction, examination of peak profiles suggested proceeding with data collection. Cell parameters were determined using reflections harvested from 3 orthogonal sets of ω scans. Final cell parameters were refined using reflections with I>10σ(I) chosen from in the entire data set. An arbitrary hemisphere of data was collected to 0.68 Å using 0.3 ω scans measured for 30 seconds in 2 correlated 30-second exposures. Data were truncated to 0.78 Å during refinement due to poor data agreement at higher resolution; 100 % of the unique data was measured. All data were corrected for Lorentz and polarization effects. No absorption correction was performed. Structure solution via direct methods in non-centrosymmetric space group P2 1 revealed the non-hydrogen structure. All non-hydrogen atoms were refined with parameters for anisotropic thermal motion. Hydrogen atoms were placed at calculated geometries and allowed to ride on the position of the parent atom. Hydrogen thermal parameters were set to 1.2 times the equivalent isotropic thermal parameter of the parent atom. Absolute structure was determined from a known stereocenter. Calculation of absolute structure by the method of Flack was indeterminate on this light atom structure. No significant features were present in the final difference electron density map.

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