- 1 - c17h30o4 : Mar 30 18:08:08 2001 =========================================== SUPPLEMENTARY MATERIAL FOR THE ACID DERIVATIVE OF Z-SYN 1,3 DIOXOLANE 4 R1 = CO2ME, R2 = CH3(CH2)5, R3 = H =========================================== BELONGING TO THE PAPER Alkynoates as a Source of Reactive Alkylinides for Aldehyde Addition Reactions Pedro de Armas*§, Fernando García-Tellado*§, José J. Marrero-Tellado*‡, David Tejedor‡, Miguel A. Maestro(, Javier Gonzalez-Platas( §Instituto de Productos Naturales y Agrobiología, CSIC. Avda. Astrofísico Fco. Sánchez 3. 38206 La Laguna. Santa Cruz de Tenerife. Spain. ‡Instituto Universitario de Bioorgánica "Antonio González". Avda Astrofísico Fco. Sánchez 2. 38206 La Laguna. Santa Cruz de Tenerife. Spain. (Servicio de Rayos X de Apoyo a la Investigación. Edfco. Anexo Facultad de Ciencias. Universidad Da Coruña. E-15071. A Coruña. Spain. ( Dpto. Física Fundamental II Servicio Integrado de Difracción (SIDIX). Universidad de La Laguna. Tenerife C o n t e n t s =============== Table S1 - Crystal Data and Details of the Structure Determination for: c17h30o4 Table S2 - Final Coordinates and Equivalent Isotropic Displacement Parameters of the non-Hydrogen atoms for: c17h30o4 Table S3 - Hydrogen Atom Positions and Isotropic Displacement Parameters for: c17h30o4 Table S4 - (An)isotropic Displacement Parameters for: c17h30o4 Table S5 - Bond Distances (Angstrom) for: c17h30o4 Table S6 - Bond Angles (Degrees) for: c17h30o4 Table S7 - Torsion Angles (Degrees) for: c17h30o4 Table S8 - Contact Distances(Angstrom) for: c17h30o4 Table S9 - Hydrogen Bonds (Angstrom, Deg) for: c17h30o4 - 2 - Table S1 - Crystal Data and Details of the Structure Determination for: c17h30o4 Crystal Data Formula C17 H30 O4 Formula Weight 298.39 Crystal System Triclinic Space group P-1 (No. 2) a, b, c [Angstrom] 8.6530(10) 10.035(2) 12.381(2) alpha, beta, gamma [deg] 102.262(12) 110.021(11) 103.180(10) V [Ang**3] 932.6(3) Z 2 D(calc) [g/cm**3] 1.063 Mu(MoKa) [ /mm ] 0.074 F(000) 328 Crystal Size [mm] 0.01 x 0.15 x 0.31 Data Collection Temperature (K) 293 Radiation [Angstrom] MoKa 0.71073 Theta Min-Max [Deg] 2.4, 25.9 Dataset -10: 0 ; -11: 12 ; -14: 15 Tot., Uniq. Data, R(int) 3873, 3621, 0.011 Observed data [I > 2.0 sigma(I)] 1941 Refinement Nref, Npar 3621, 200 R, wR2, S 0.0744, 0.2188, 1.05 w = 1/[\s^2^(Fo^2^)+(0.1207P)^2^+0.2423P] where P=(Fo^2^+2Fc^2^)/3 Max. and Av. Shift/Error 0.00, 0.00 Min. and Max. Resd. Dens. [e/Ang^3] -0.24, 0.40 - 3 - Table S2 - Final Coordinates and Equivalent Isotropic Displacement Parameters of the non-Hydrogen atoms for: c17h30o4 Atom x y z U(eq) [Ang^2] ---- --- --- --- ----------- O1 0.6512(3) 0.4757(2) 0.1429(2) 0.0940(9) O3 0.8100(3) 0.3692(2) 0.0648(2) 0.0891(9) O8 0.9549(3) 0.1523(2) 0.0226(2) 0.0957(9) O9 0.8310(3) -0.0500(2) 0.0487(2) 0.1058(10) C2 0.7460(4) 0.4918(3) 0.0716(4) 0.0950(14) C4 0.7067(3) 0.2667(3) 0.0863(3) 0.0751(10) C5 0.5749(4) 0.3238(3) 0.1155(3) 0.0820(11) C6 0.7217(4) 0.1366(3) 0.0814(3) 0.0790(10) C7 0.8442(4) 0.0813(3) 0.0487(3) 0.0757(10) C10 0.8913(5) 0.6280(4) 0.1228(4) 0.1134(18) C11 1.0145(6) 0.6508(5) 0.2470(5) 0.153(2) C12 1.1767(9) 0.7912(7) 0.3052(8) 0.211(4) C13 1.3166(12) 0.7798(9) 0.2790(9) 0.244(5) C14 1.4770(11) 0.8763(12) 0.3228(9) 0.249(6) C15 1.5969(9) 0.8614(8) 0.2725(6) 0.198(4) C16 0.5363(4) 0.2897(4) 0.2175(3) 0.0949(14) C17 0.4069(5) 0.3539(4) 0.2455(4) 0.1012(14) C18 0.3471(6) 0.2962(5) 0.3334(4) 0.1266(19) C19 0.2202(6) 0.3591(6) 0.3646(5) 0.140(3) C20 0.1570(10) 0.3069(13) 0.4487(8) 0.198(5) *C21B 0.0579(17) 0.1763(15) 0.4165(11) 0.170(6) *C21A 0.021(2) 0.331(3) 0.4580(12) 0.223(11) U(eq) = 1/3 of the trace of the orthogonalized U Tensor Starred Atom sites have a S.O.F less than 1.0 - 4 - Table S3 - Hydrogen Atom Positions and Isotropic Displacement Parameters for: c17h30o4 Atom x y z U(iso) [Ang^2] ---- --- --- --- ----------- H5 0.46610 0.28860 0.04240 0.0980 H6 0.64510 0.07530 0.10100 0.0950 H9 0.90420 -0.07430 0.02880 0.1580 H10A 0.95360 0.62930 0.07100 0.1360 H10B 0.84490 0.70740 0.12320 0.1360 H11A 0.95180 0.65250 0.29860 0.1830 H11B 1.05550 0.56850 0.24650 0.1830 H12A 1.21460 0.81990 0.39250 0.2530 H12B 1.14110 0.86760 0.27820 0.2530 H13A 1.27380 0.75710 0.19170 0.2930 H13B 1.33530 0.69340 0.29600 0.2930 H14A 1.46180 0.96890 0.32140 0.2990 H14B 1.53310 0.88400 0.40750 0.2990 H15A 1.70220 0.94230 0.31650 0.2970 H2 0.66750 0.48440 -0.00980 0.1140 H15C 1.54850 0.85760 0.18910 0.2970 H16A 0.49130 0.18570 0.19750 0.1140 H16B 0.64420 0.32490 0.28980 0.1140 H17A 0.45980 0.45790 0.27980 0.1220 H17B 0.30640 0.33270 0.17060 0.1220 H18A 0.44830 0.31600 0.40750 0.1510 H18B 0.29340 0.19220 0.29840 0.1510 H19A 0.12030 0.34000 0.28990 0.1690 H19B 0.27480 0.46300 0.39920 0.1690 H20A 0.25180 0.34830 0.52870 0.2370 H20B 0.13320 0.20330 0.42580 0.2370 - 5 - Table S3 - Hydrogen Atom Positions and Isotropic Displacement Parameters (continued) for: c17h30o4 Atom x y z U(iso) [Ang^2] ---- --- --- --- ----------- *H21D 0.03070 0.16000 0.48260 0.2540 *H21E -0.04760 0.15960 0.34800 0.2540 *H21F 0.11650 0.11140 0.39500 0.2540 H15B 1.62210 0.77390 0.27720 0.2970 *H21A -0.00230 0.29250 0.51740 0.3370 *H21B 0.04190 0.43330 0.48240 0.3370 *H21C -0.07690 0.28570 0.38100 0.3370 ======================================================= The Temperature Factor has the Form of Exp(-T) Where T = 8*(Pi**2)*U*(Sin(Theta)/Lambda)**2 for Isotropic Atoms - 6 - Table S4 - (An)isotropic Displacement Parameters for: c17h30o4 Atom U(1,1) or U U(2,2) U(3,3) U(2,3) U(1,3) U(1,2) ---- ------ ------ ------ ------ ------ ------ O1 0.0927(14) 0.0720(13) 0.1417(19) 0.0455(13) 0.0618(14) 0.0388(11) O3 0.0918(14) 0.0665(12) 0.1388(19) 0.0505(12) 0.0635(13) 0.0380(10) O8 0.1022(15) 0.0684(12) 0.151(2) 0.0543(13) 0.0744(15) 0.0372(11) O9 0.1140(17) 0.0622(12) 0.176(2) 0.0523(13) 0.0857(17) 0.0372(12) C2 0.098(2) 0.078(2) 0.145(3) 0.059(2) 0.065(2) 0.0480(18) C4 0.0686(16) 0.0671(17) 0.095(2) 0.0343(15) 0.0337(15) 0.0237(13) C5 0.0726(17) 0.0690(18) 0.111(2) 0.0345(16) 0.0388(17) 0.0277(14) C6 0.0726(17) 0.0624(16) 0.106(2) 0.0334(15) 0.0388(16) 0.0197(13) C7 0.0776(17) 0.0553(15) 0.096(2) 0.0296(14) 0.0348(16) 0.0209(13) C10 0.115(3) 0.078(2) 0.180(4) 0.061(2) 0.078(3) 0.045(2) C11 0.137(4) 0.091(3) 0.182(5) 0.035(3) 0.027(4) 0.017(3) C12 0.167(6) 0.137(5) 0.287(9) 0.047(5) 0.074(6) 0.023(4) C13 0.194(8) 0.230(9) 0.296(10) 0.093(7) 0.131(8) -0.006(7) C14 0.178(7) 0.329(12) 0.293(10) 0.138(9) 0.125(8) 0.097(8) C15 0.179(6) 0.232(8) 0.186(6) 0.095(5) 0.077(5) 0.044(5) C16 0.091(2) 0.093(2) 0.124(3) 0.050(2) 0.054(2) 0.0420(18) C17 0.099(2) 0.103(2) 0.123(3) 0.047(2) 0.058(2) 0.042(2) C18 0.129(3) 0.156(4) 0.144(3) 0.077(3) 0.077(3) 0.075(3) C19 0.148(4) 0.180(5) 0.143(4) 0.074(3) 0.085(3) 0.083(4) C20 0.183(6) 0.280(10) 0.208(7) 0.123(7) 0.122(6) 0.107(8) C21B 0.153(9) 0.156(11) 0.188(11) 0.039(8) 0.086(8) 0.019(8) C21A 0.177(13) 0.39(3) 0.158(11) 0.079(14) 0.105(10) 0.142(15) ======================================================= The Temperature Factor has the Form of Exp(-T) Where T = 8*(Pi**2)*U*(Sin(Theta)/Lambda)**2 for Isotropic Atoms T = 2*(Pi**2)*Sumij(h(i)*h(j)*U(i,j)*Astar(i)*Astar(j)), for Anisotropic Atoms. Astar(i) are Reciprocal Axial Lengths and h(i) are the Reflection Indices. - 7 - Table S5 - Bond Distances (Angstrom) for: c17h30o4 O1 -C2 1.405(5) C11 -H11A 0.9694 O1 -C5 1.429(4) C11 -H11B 0.9700 O3 -C2 1.458(4) C12 -H12A 0.9699 O3 -C4 1.337(4) C12 -H12B 0.9698 O8 -C7 1.236(4) C13 -H13A 0.9696 O9 -C7 1.296(4) C13 -H13B 0.9697 O9 -H9 0.8204 C14 -H14A 0.9706 C2 -C10 1.467(6) C14 -H14B 0.9702 C4 -C6 1.332(4) C15 -H15A 0.9597 C4 -C5 1.501(5) C15 -H15B 0.9603 C5 -C16 1.498(5) C15 -H15C 0.9607 C6 -C7 1.436(5) C16 -H16A 0.9701 C10 -C11 1.473(7) C16 -H16B 0.9700 C11 -C12 1.565(10) C17 -H17A 0.9695 C12 -C13 1.378(14) C17 -H17B 0.9701 C13 -C14 1.344(15) C18 -H18A 0.9701 C14 -C15 1.400(13) C18 -H18B 0.9704 C16 -C17 1.513(6) C19 -H19A 0.9701 C17 -C18 1.518(7) C19 -H19B 0.9700 C18 -C19 1.502(8) C20 -H20A 0.9695 C19 -C20 1.466(12) C20 -H20B 0.9699 C20 -C21B 1.28(2) C21A -H21C 0.9594 C20 -C21A 1.29(2) C21A -H21A 0.9578 C2 -H2 0.9793 C21A -H21B 0.9613 C5 -H5 0.9795 C21B -H20B 0.6050 C6 -H6 0.9296 C21B -H21D 0.9608 C10 -H10A 0.9691 C21B -H21E 0.9594 C10 -H10B 0.9704 C21B -H21F 0.9600 - 8 - Table S6 - Bond Angles (Degrees) for: c17h30o4 C2 -O1 -C5 106.1(3) O3 -C2 -H2 109.40 C2 -O3 -C4 108.0(3) C10 -C2 -H2 109.41 C7 -O9 -H9 109.46 O1 -C5 -H5 108.94 O1 -C2 -O3 104.2(3) C4 -C5 -H5 108.88 O1 -C2 -C10 113.6(3) C16 -C5 -H5 108.91 O3 -C2 -C10 110.6(3) C4 -C6 -H6 116.79 O3 -C4 -C6 124.4(3) C7 -C6 -H6 116.65 C5 -C4 -C6 127.1(3) C2 -C10 -H10A 108.91 O3 -C4 -C5 108.5(3) C2 -C10 -H10B 108.86 O1 -C5 -C16 111.3(3) C11 -C10 -H10A 108.91 C4 -C5 -C16 116.5(3) C11 -C10 -H10B 108.84 O1 -C5 -C4 102.0(3) H10A -C10 -H10B 107.74 C4 -C6 -C7 126.6(3) C10 -C11 -H11A 108.28 O8 -C7 -C6 123.2(3) C10 -C11 -H11B 108.25 O9 -C7 -C6 114.9(3) C12 -C11 -H11A 108.26 O8 -C7 -O9 121.8(3) C12 -C11 -H11B 108.28 C2 -C10 -C11 113.4(4) H11A -C11 -H11B 107.37 C10 -C11 -C12 116.1(5) C11 -C12 -H12A 108.42 C11 -C12 -C13 115.4(7) C11 -C12 -H12B 108.43 C12 -C13 -C14 129.2(9) C13 -C12 -H12A 108.44 C13 -C14 -C15 123.0(10) C13 -C12 -H12B 108.44 C5 -C16 -C17 114.2(3) H12A -C12 -H12B 107.49 C16 -C17 -C18 112.6(4) C12 -C13 -H13A 105.02 C17 -C18 -C19 114.1(4) C12 -C13 -H13B 105.02 C18 -C19 -C20 116.6(6) C14 -C13 -H13A 104.94 C19 -C20 -C21B 120.4(9) C14 -C13 -H13B 104.92 C19 -C20 -C21A 119.3(13) H13A -C13 -H13B 105.86 O1 -C2 -H2 109.43 C13 -C14 -H14A 106.57 - 9 - Table S6 - Bond Angles (Degrees) (continued) for: c17h30o4 C13 -C14 -H14B 106.60 C20 -C19 -H19A 108.13 C15 -C14 -H14A 106.61 C20 -C19 -H19B 108.16 C15 -C14 -H14B 106.61 H19A -C19 -H19B 107.29 H14A -C14 -H14B 106.49 C19 -C20 -H20A 107.45 C14 -C15 -H15A 109.53 C19 -C20 -H20B 107.45 C14 -C15 -H15B 109.46 C21B -C20 -H20A 119.01 C14 -C15 -H15C 109.48 C21B -C20 -H20B 26.88 H15A -C15 -H15B 109.50 H20A -C20 -H20B 106.97 H15A -C15 -H15C 109.45 C21A -C20 -H20A 107.62 H15B -C15 -H15C 109.41 C21A -C20 -H20B 107.44 C5 -C16 -H16A 108.73 H21B -C21A -H21C 109.46 C5 -C16 -H16B 108.73 C20 -C21A -H21B 109.27 C17 -C16 -H16A 108.66 C20 -C21A -H21C 109.39 C17 -C16 -H16B 108.71 C20 -C21A -H21A 109.45 H16A -C16 -H16B 107.62 H21A -C21A -H21C 109.71 C16 -C17 -H17A 109.09 H21A -C21A -H21B 109.54 C16 -C17 -H17B 109.04 C20 -C21B -H21E 109.53 C18 -C17 -H17A 109.03 C20 -C21B -H21D 109.43 C18 -C17 -H17B 109.07 H21D -C21B -H21F 109.39 H17A -C17 -H17B 107.85 H21E -C21B -H21F 109.47 C17 -C18 -H18A 108.71 C20 -C21B -H21F 109.50 C17 -C18 -H18B 108.73 H20B -C21B -H21D 118.90 C19 -C18 -H18A 108.74 H20B -C21B -H21E 130.70 C19 -C18 -H18B 108.73 H20B -C21B -H21F 63.48 H18A -C18 -H18B 107.61 H21D -C21B -H21E 109.50 C18 -C19 -H19A 108.14 C20 -C21B -H20B 46.46 C18 -C19 -H19B 108.13 - 10 - Table S7 - Torsion Angles (Degrees) for: c17h30o4 C5 -O1 -C2 -O3 -33.6(3) C5 -O1 -C2 -C10 -154.0(3) C2 -O1 -C5 -C4 30.9(3) C2 -O1 -C5 -C16 155.8(3) C4 -O3 -C2 -O1 22.7(4) C4 -O3 -C2 -C10 145.2(3) C2 -O3 -C4 -C5 -3.3(4) C2 -O3 -C4 -C6 176.5(3) O1 -C2 -C10 -C11 55.8(5) O3 -C2 -C10 -C11 -61.0(5) O3 -C4 -C5 -C16 -138.2(3) C6 -C4 -C5 -O1 163.4(3) O3 -C4 -C5 -O1 -16.8(3) C6 -C4 -C5 -C16 42.0(5) O3 -C4 -C6 -C7 -2.4(6) C5 -C4 -C6 -C7 177.4(3) C4 -C5 -C16 -C17 178.2(3) O1 -C5 -C16 -C17 61.8(4) C4 -C6 -C7 -O9 -178.9(3) C4 -C6 -C7 -O8 1.3(6) C2 -C10 -C11 -C12 177.6(5) C10 -C11 -C12 -C13 -85.9(8) C11 -C12 -C13 -C14 -174.0(10) C12 -C13 -C14 -C15 -168.1(10) C5 -C16 -C17 -C18 169.9(3) C16 -C17 -C18 -C19 179.2(4) C17 -C18 -C19 -C20 179.7(6) C18 -C19 -C20 -C21B -68.0(12) - 11 - Table S8 - Contact Distances(Angstrom) for: c17h30o4 O3 .O8 2.792(3) C21B .H18B 2.8822 O8 .O9_d 2.621(4) H2 .O1_a 2.8553 O8 .C7_d 3.365(4) H5 .H17B 2.4713 O8 .O3 2.792(3) H5 .O9_f 2.7703 O9 .O8_d 2.621(4) H6 .C16 2.8515 O1 .H17A 2.7502 H6 .H16A 2.3717 O1 .H11A 2.5766 H9 .C7_d 2.6715 O1 .H2_a 2.8553 H9 .O8_d 1.8053 O3 .H11B 2.5402 H9 .O9_d 2.9047 O3 .H13A_b 2.9175 H9 .H9_d 2.3696 O8 .H17B_c 2.8548 H10A .C13 3.0700 O8 .H10A_b 2.7729 H10A .H13A 2.5070 O8 .H9_d 1.8053 H10A .O8_b 2.7729 O9 .H10B_e 2.7935 H10B .H12B 2.5058 O9 .H5_f 2.7703 H10B .O9_i 2.7935 O9 .H9_d 2.9047 H11A .C21A_g 2.9067 C7 .O8_d 3.365(4) H11A .O1 2.5766 C21A .C21A_l 3.47(4) H11A .H21A_g 2.0880 C6 .H16A 2.8971 H11B .O3 2.5402 C7 .H9_d 2.6715 H11B .H13B 2.2544 C10 .H13A 3.0004 H12B .H10B 2.5058 C11 .H21A_g 2.8943 H12B .H14A 2.5469 C13 .H10A 3.0700 H13A .H10A 2.5070 C16 .H6 2.8515 H13A .C10 3.0004 C18 .H21F 2.8209 H13A .H15C 2.3751 C21A .H21B_l 2.5604 H13A .O3_b 2.9175 C21A .H11A_g 2.9067 H13B .H11B 2.2544 C21B .H15A_h 3.0627 H13B .H15B 2.5351 - 12 - Table S8 - Contact Distances(Angstrom) (continued) for: c17h30o4 H14A .H12B 2.5469 H18B .H16A 2.4451 H15A .C21B_j 3.0627 H19A .H17B 2.5331 H15A .H21E_j 2.5499 H19A .H21E 2.4443 H15B .H13B 2.5351 H19A .H21C 2.3740 H15C .H13A 2.3751 H19B .H17A 2.5251 H16A .C6 2.8971 H19B .H21B 2.5474 H16A .H6 2.3717 H20B .H18B 2.4321 H16A .H18B 2.4451 H21A .C11_g 2.8943 H16B .H18A 2.5851 H21A .H11A_g 2.0880 H16B .H21C_c 2.4514 H21B .H19B 2.5474 H17A .H19B 2.5251 H21B .C21A_l 2.5604 H17A .O1 2.7502 H21B .H21B_l 1.7085 H17B .O8_k 2.8548 H21C .H19A 2.3740 H17B .H5 2.4713 H21C .H16B_k 2.4514 H17B .H19A 2.5331 H21E .H15A_h 2.5499 H18A .H16B 2.5851 H21E .H19A 2.4443 H18B .H20B 2.4321 H21F .C18 2.8209 H18B .H21F 2.3517 H21F .H18B 2.3517 H18B .C21B 2.8822 - 13 - Table S9 - Hydrogen Bonds (Angstrom, Deg) for: c17h30o4 O9 -- H9 .. O8 0.8204 1.8053 2.621(4) 172.27 2_755 - 14 - Translation of Symmetry Code to Equiv.Pos a =[ 2665.00 ] = 1-x,1-y,-z b =[ 2765.00 ] = 2-x,1-y,-z c =[ 1655.00 ] = 1+x,y,z d =[ 2755.00 ] = 2-x,-y,-z e =[ 1545.00 ] = x,-1+y,z f =[ 2655.00 ] = 1-x,-y,-z g =[ 2666.00 ] = 1-x,1-y,1-z h =[ 1345.00 ] = -2+x,-1+y,z i =[ 1565.00 ] = x,1+y,z j =[ 1765.00 ] = 2+x,1+y,z k =[ 1455.00 ] = -1+x,y,z l =[ 2566.00 ] = -x,1-y,1-z