Supplementary Material (ESI) for Organic and Biomolecular Chemistry This journal is (C) The Royal Society of Chemistry 2006 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'A. Marsh' 'Andrew J. Clark' 'G.J. Clarkson' 'Timothy R. Smith' 'Paul C. Taylor' _publ_contact_author_name A.Marsh _publ_contact_author_address ; Department of Chemistry University of Warwick COVENTRY CV4 7AL UNITED KINGDOM ; _publ_contact_author_email A.MARSH@WARWICK.AC.UK _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Concise Enantioselective Synthesis of Abscisic Acid and Analogues ; # Attachment 'ts2.cif' data_ts2 _database_code_depnum_ccdc_archive 'CCDC 618045' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C15 H22 O3' _chemical_formula_weight 250.33 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 7.6916(3) _cell_length_b 11.7602(5) _cell_length_c 8.2773(4) _cell_angle_alpha 90.00 _cell_angle_beta 95.392(3) _cell_angle_gamma 90.00 _cell_volume 745.41(6) _cell_formula_units_Z 2 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used 1438 _cell_measurement_theta_min 4.67 _cell_measurement_theta_max 67.4 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.115 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 272 _exptl_absorpt_coefficient_mu 0.610 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7002 _exptl_absorpt_correction_T_max 0.9939 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cooler (Cosier & Glazer, 1986). The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of three sets of exposures with different \f angles for the crystal; each 10 s exposure covered 0.3\% in \w. The crystal-to-detector distance was 5.0 cm. Coverage of the unique Set is over 97% complete to at least 26\% in \q. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 (or 1.5 for methylor OH H-atoms) times the equivalent isotropic displacement parameter of the atom to which they are attached. The crystals were very thin plates and weakly diffracting. ; _diffrn_ambient_temperature 273(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Siemens SMART diffractometer' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8.192 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% nil _diffrn_reflns_number 4874 _diffrn_reflns_av_R_equivalents 0.0301 _diffrn_reflns_av_sigmaI/netI 0.0370 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 5.37 _diffrn_reflns_theta_max 70.71 _reflns_number_total 2247 _reflns_number_gt 2051 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1994)' _computing_cell_refinement 'SAINT (Siemens, 1995)' _computing_data_reduction 'SAINT (Siemens, 1995)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL (Sheldrick, 1997)' _computing_publication_material 'SHELXTL (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0476P)^2^+0.0177P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881, 849' _refine_ls_abs_structure_Flack 0.0(2) _chemical_absolute_configuration rmad _refine_ls_number_reflns 2247 _refine_ls_number_parameters 171 _refine_ls_number_restraints 19 _refine_ls_R_factor_all 0.0387 _refine_ls_R_factor_gt 0.0348 _refine_ls_wR_factor_ref 0.0879 _refine_ls_wR_factor_gt 0.0846 _refine_ls_goodness_of_fit_ref 1.060 _refine_ls_restrained_S_all 1.089 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.7559(3) 0.6749(2) 0.5471(3) 0.0819(7) Uani 1 1 d U . . H1 H 0.8694 0.7022 0.5467 0.098 Uiso 1 1 calc R . . C2 C 0.6142(2) 0.64079(18) 0.5475(2) 0.0565(5) Uani 1 1 d . . . O3 O 0.43071(18) 0.49909(13) 0.64508(18) 0.0642(4) Uani 1 1 d . . . H3A H 0.530(4) 0.466(3) 0.653(4) 0.096 Uiso 1 1 d . . . C3 C 0.4334(2) 0.59578(16) 0.5427(2) 0.0477(4) Uani 1 1 d . . . C4 C 0.3221(2) 0.68793(17) 0.6130(2) 0.0489(4) Uani 1 1 d . . . C5 C 0.2290(2) 0.76075(16) 0.5179(2) 0.0499(4) Uani 1 1 d . . . H5A H 0.1661 0.8160 0.5679 0.060 Uiso 1 1 calc R . . C6 C 0.2176(2) 0.76086(16) 0.3376(2) 0.0497(4) Uani 1 1 d . . . O7 O 0.03962(15) 0.74010(12) 0.27812(17) 0.0585(4) Uani 1 1 d . . . C8 C -0.0033(2) 0.81565(17) 0.1448(2) 0.0543(4) Uani 1 1 d . . . H8A H 0.0405 0.7845 0.0465 0.065 Uiso 1 1 calc R . . C9 C 0.1004(3) 0.92061(17) 0.1984(3) 0.0590(5) Uani 1 1 d . . . H9A H 0.0382 0.9632 0.2770 0.071 Uiso 1 1 calc R . . O10 O 0.25625(17) 0.87220(12) 0.27853(19) 0.0654(4) Uani 1 1 d . . . C11 C 0.3411(3) 0.67692(19) 0.2705(2) 0.0583(5) Uani 1 1 d . . . H11A H 0.4549 0.7123 0.2697 0.070 Uiso 1 1 calc R . . H11B H 0.2991 0.6597 0.1591 0.070 Uiso 1 1 calc R . . C12 C 0.3618(3) 0.56531(18) 0.3662(2) 0.0553(5) Uani 1 1 d . . . C13 C 0.4909(4) 0.4883(3) 0.2874(3) 0.0875(8) Uani 1 1 d U . . H13A H 0.4472 0.4728 0.1772 0.131 Uiso 1 1 calc R . . H13B H 0.5044 0.4182 0.3467 0.131 Uiso 1 1 calc R . . H13C H 0.6020 0.5258 0.2892 0.131 Uiso 1 1 calc R . . C14 C 0.1879(3) 0.5023(2) 0.3686(3) 0.0733(6) Uani 1 1 d . . . H14A H 0.1398 0.4879 0.2593 0.110 Uiso 1 1 calc R . . H14B H 0.1080 0.5481 0.4229 0.110 Uiso 1 1 calc R . . H14C H 0.2069 0.4315 0.4251 0.110 Uiso 1 1 calc R . . C15 C -0.1983(3) 0.8279(2) 0.1193(3) 0.0760(7) Uani 1 1 d . . . H15A H -0.2504 0.7546 0.0986 0.114 Uiso 1 1 calc R . . H15B H -0.2286 0.8770 0.0283 0.114 Uiso 1 1 calc R . . H15C H -0.2406 0.8601 0.2148 0.114 Uiso 1 1 calc R . . C16 C 0.1474(4) 0.9991(2) 0.0661(3) 0.0894(8) Uani 1 1 d U . . H16A H 0.2209 1.0590 0.1123 0.134 Uiso 1 1 calc R . . H16B H 0.0429 1.0312 0.0119 0.134 Uiso 1 1 calc R . . H16C H 0.2085 0.9573 -0.0105 0.134 Uiso 1 1 calc R . . C17 C 0.3326(3) 0.6946(2) 0.7941(3) 0.0755(6) Uani 1 1 d . . . H17A H 0.2696 0.7602 0.8256 0.113 Uiso 1 1 calc R . . H17B H 0.4527 0.7006 0.8369 0.113 Uiso 1 1 calc R . . H17C H 0.2823 0.6273 0.8361 0.113 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0514(12) 0.0767(15) 0.119(2) 0.0165(15) 0.0179(11) -0.0060(11) C2 0.0507(11) 0.0555(11) 0.0643(12) 0.0120(9) 0.0106(8) 0.0040(9) O3 0.0560(8) 0.0591(9) 0.0776(10) 0.0262(7) 0.0066(6) 0.0002(6) C3 0.0477(9) 0.0451(10) 0.0510(10) 0.0069(8) 0.0077(7) 0.0002(7) C4 0.0499(9) 0.0500(10) 0.0483(10) -0.0011(8) 0.0122(7) -0.0064(8) C5 0.0442(9) 0.0454(10) 0.0615(11) -0.0054(8) 0.0119(7) 0.0001(8) C6 0.0441(9) 0.0433(10) 0.0617(11) 0.0091(8) 0.0050(7) -0.0005(8) O7 0.0446(7) 0.0562(8) 0.0736(9) 0.0121(7) -0.0002(5) -0.0033(6) C8 0.0533(10) 0.0547(11) 0.0545(11) -0.0017(9) 0.0025(7) 0.0071(8) C9 0.0663(12) 0.0500(11) 0.0590(12) 0.0054(9) -0.0029(8) 0.0086(9) O10 0.0540(7) 0.0540(8) 0.0856(10) 0.0218(7) -0.0067(6) -0.0072(6) C11 0.0580(11) 0.0701(13) 0.0475(10) 0.0057(10) 0.0091(7) 0.0116(10) C12 0.0601(11) 0.0525(11) 0.0528(11) -0.0033(9) 0.0038(8) 0.0136(9) C13 0.0978(18) 0.0883(18) 0.0757(15) -0.0166(14) 0.0043(12) 0.0382(15) C14 0.0807(14) 0.0505(12) 0.0840(16) -0.0053(11) -0.0166(11) -0.0023(11) C15 0.0575(13) 0.0887(18) 0.0795(16) 0.0025(13) -0.0064(10) 0.0104(11) C16 0.117(2) 0.0699(15) 0.0774(16) 0.0232(13) -0.0122(13) -0.0142(14) C17 0.0923(16) 0.0826(17) 0.0535(13) -0.0015(12) 0.0181(10) -0.0044(13) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 C2 1.162(3) . ? C1 H1 0.9300 . ? C2 C3 1.485(3) . ? O3 C3 1.420(2) . ? O3 H3A 0.86(3) . ? C3 C4 1.530(3) . ? C3 C12 1.554(3) . ? C4 C5 1.326(3) . ? C4 C17 1.496(3) . ? C5 C6 1.487(3) . ? C5 H5A 0.9300 . ? C6 O7 1.432(2) . ? C6 O10 1.438(2) . ? C6 C11 1.512(3) . ? O7 C8 1.431(2) . ? C8 C15 1.502(3) . ? C8 C9 1.513(3) . ? C8 H8A 0.9800 . ? C9 O10 1.433(2) . ? C9 C16 1.503(3) . ? C9 H9A 0.9800 . ? C11 C12 1.533(3) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 C14 1.531(3) . ? C12 C13 1.533(3) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C15 H15A 0.9600 . ? C15 H15B 0.9600 . ? C15 H15C 0.9600 . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C17 H17A 0.9600 . ? C17 H17B 0.9600 . ? C17 H17C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 C1 H1 180.0 . . ? C1 C2 C3 178.2(2) . . ? C3 O3 H3A 110(2) . . ? O3 C3 C2 109.62(15) . . ? O3 C3 C4 107.46(15) . . ? C2 C3 C4 107.08(16) . . ? O3 C3 C12 110.66(15) . . ? C2 C3 C12 110.82(15) . . ? C4 C3 C12 111.08(15) . . ? C5 C4 C17 122.44(19) . . ? C5 C4 C3 121.44(16) . . ? C17 C4 C3 116.04(18) . . ? C4 C5 C6 125.04(17) . . ? C4 C5 H5A 117.5 . . ? C6 C5 H5A 117.5 . . ? O7 C6 O10 105.05(14) . . ? O7 C6 C5 108.04(14) . . ? O10 C6 C5 110.34(16) . . ? O7 C6 C11 112.09(16) . . ? O10 C6 C11 108.20(15) . . ? C5 C6 C11 112.85(15) . . ? C8 O7 C6 107.64(13) . . ? O7 C8 C15 108.83(17) . . ? O7 C8 C9 101.74(14) . . ? C15 C8 C9 117.02(18) . . ? O7 C8 H8A 109.6 . . ? C15 C8 H8A 109.6 . . ? C9 C8 H8A 109.6 . . ? O10 C9 C16 109.45(19) . . ? O10 C9 C8 101.91(15) . . ? C16 C9 C8 116.35(19) . . ? O10 C9 H9A 109.6 . . ? C16 C9 H9A 109.6 . . ? C8 C9 H9A 109.6 . . ? C9 O10 C6 109.17(14) . . ? C6 C11 C12 114.06(15) . . ? C6 C11 H11A 108.7 . . ? C12 C11 H11A 108.7 . . ? C6 C11 H11B 108.7 . . ? C12 C11 H11B 108.7 . . ? H11A C11 H11B 107.6 . . ? C14 C12 C13 108.7(2) . . ? C14 C12 C11 111.86(16) . . ? C13 C12 C11 109.02(18) . . ? C14 C12 C3 109.40(16) . . ? C13 C12 C3 110.46(16) . . ? C11 C12 C3 107.36(16) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C8 C15 H15A 109.5 . . ? C8 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C8 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C9 C16 H16A 109.5 . . ? C9 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C9 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C4 C17 H17A 109.5 . . ? C4 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C4 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O3 H3A O10 0.86(3) 2.01(3) 2.853(2) 166(3) 2_646 _diffrn_measured_fraction_theta_max 0.922 _diffrn_reflns_theta_full 67.70 _diffrn_measured_fraction_theta_full 0.953 _refine_diff_density_max 0.101 _refine_diff_density_min -0.139 _refine_diff_density_rms 0.031