# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2011 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Krische, Michael' _publ_contact_author_name 'Krische, Michael' _publ_contact_author_email mkrische@mail.utexas.edu _publ_section_title ; Catalytic Enantioselective Grignard Nozaki-Hiyama Methallylation from the Alcohol Oxidation Level: Chloride Compensates for p-Complex Instability ; # Attachment '- ahbr1.cif' data_shelxl _database_code_depnum_ccdc_archive 'CCDC 835997' #TrackingRef '- ahbr1.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_absolute_configuration ad # syn absolute configuration from synthetic procedure # ad absolute configuration from anomalous dispersion effects # rm absolute configuration from reference to a chiral # reference molecule of known abs. conf. # Hooft, R. W. W., Straver, L. H. and Spek, A. L. (2008). J. Appl. Cryst., # 41, 96-103. Determination of absolute structure using Bayesian # statistics on Bijvoet differences. _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C11 H13 Br O' _chemical_formula_sum 'C11 H13 Br O' _chemical_formula_weight 241.12 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 '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 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 9.2407(9) _cell_length_b 5.1056(6) _cell_length_c 11.6424(12) _cell_angle_alpha 90.00 _cell_angle_beta 105.335(4) _cell_angle_gamma 90.00 _cell_volume 529.72(10) _cell_formula_units_Z 2 _cell_measurement_temperature 153(2) _cell_measurement_reflns_used 1629 _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 30.0 _exptl_crystal_description needles _exptl_crystal_colour colorless _exptl_crystal_size_max 0.52 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.512 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 244 _exptl_absorpt_coefficient_mu 3.839 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min 0.413 _exptl_absorpt_correction_T_max 0.867 _exptl_absorpt_process_details ; N.W. Alcock (1970). Cryst. Computing, p271 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 153(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method \w-scans _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8793 _diffrn_reflns_av_R_equivalents 0.0654 _diffrn_reflns_av_sigmaI/netI 0.0652 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.29 _diffrn_reflns_theta_max 30.00 _reflns_number_total 3030 _reflns_number_gt 2188 _reflns_threshold_expression >2sigma(I) _publ_section_references ; Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C., Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R. Sir97. (1999) J. Appl. Cryst. 32, 115-119. Farrugia, L. J. (1999) J. Appl. Cryst., 32, 837-838. An Integrated System of Windows Programs for the Solution, Refinement and Analysis of Single Crystal X-ray Diffraction Data. Hooft, R. W. W., Straver, L. H. and Spek, A. L. (2008). J. Appl. Cryst., 41, 96-103. Determination of absolute structure using Bayesian statistics on Bijvoet differences. Otwinowski, Z. and Minor, W. (1997). Methods in Enzymology, 276, Macromolecular Crystallography, part A, 307-326, C. W. Carter, Jr. and R. M. Sweets, Eds., Academic Press. Sheldrick, G. M. (2008). SHELXL-97. Acat Cryst., A64, 112-122. Spek, A. L. (1998) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. ; _computing_data_collection 'Collect software, Nonius B.V. 1998' _computing_cell_refinement 'Collect software, Nonius B.V. 1998' _computing_data_reduction ; DENZO and Scalepack (Otwinoski and Minor, 1997) ; _computing_structure_solution ; SIR97 - Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C., Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R. ; _computing_structure_refinement 'XL SHELXTL/PC, Siemens Analytical' _computing_molecular_graphics 'XP SHELXTL/PC, Siemens Analytical' _computing_publication_material ? _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. The absolute configuration was determined by the method of Flack (Flack, 1983) and corroborated by use of the Hooft y-parameter (Hooft, Straver and Spek, 2008). The Hooft y-parameter refined to -0.03(1). ; _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^)+(0.0223P)^2^+0.3520P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.036(14) _refine_ls_number_reflns 3030 _refine_ls_number_parameters 120 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0849 _refine_ls_R_factor_gt 0.0469 _refine_ls_wR_factor_ref 0.0915 _refine_ls_wR_factor_gt 0.0770 _refine_ls_goodness_of_fit_ref 1.130 _refine_ls_restrained_S_all 1.130 _refine_ls_shift/su_max 0.001 _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 Br1 Br 0.63001(4) 0.53572(12) 0.95773(3) 0.04812(14) Uani 1 1 d . . . O1 O 1.0137(3) 0.9129(5) 0.5515(2) 0.0277(5) Uani 1 1 d . . . H1O H 1.0037 0.7633 0.5203 0.042 Uiso 1 1 calc R . . C1 C 0.7649(4) 0.6513(8) 0.8694(3) 0.0327(9) Uani 1 1 d . . . C2 C 0.8594(5) 0.8578(7) 0.9105(3) 0.0325(9) Uani 1 1 d . . . H2 H 0.8565 0.9464 0.9816 0.039 Uiso 1 1 calc R . . C3 C 0.9598(4) 0.9355(7) 0.8463(3) 0.0296(8) Uani 1 1 d . . . H3 H 1.0262 1.0775 0.8744 0.036 Uiso 1 1 calc R . . C4 C 0.9643(4) 0.8089(7) 0.7421(3) 0.0228(7) Uani 1 1 d . . . C5 C 0.8640(4) 0.6039(7) 0.7013(3) 0.0335(10) Uani 1 1 d . . . H5 H 0.8641 0.5184 0.6288 0.040 Uiso 1 1 calc R . . C6 C 0.7642(4) 0.5226(13) 0.7647(3) 0.0351(8) Uani 1 1 d . . . H6 H 0.6969 0.3818 0.7367 0.042 Uiso 1 1 calc R . . C7 C 1.0790(4) 0.8893(7) 0.6771(3) 0.0248(7) Uani 1 1 d . . . H7 H 1.1184 1.0655 0.7077 0.030 Uiso 1 1 calc R . . C8 C 1.2122(4) 0.6989(7) 0.7026(3) 0.0258(8) Uani 1 1 d . . . H8A H 1.2529 0.6814 0.7899 0.031 Uiso 1 1 calc R . . H8B H 1.1759 0.5243 0.6706 0.031 Uiso 1 1 calc R . . C9 C 1.3371(4) 0.7839(7) 0.6493(3) 0.0291(8) Uani 1 1 d . . . C10 C 1.3613(5) 0.6666(9) 0.5550(4) 0.0405(10) Uani 1 1 d . . . H10A H 1.4396 0.7259 0.5226 0.049 Uiso 1 1 calc R . . H10B H 1.3003 0.5230 0.5196 0.049 Uiso 1 1 calc R . . C11 C 1.4306(4) 1.0126(12) 0.7090(3) 0.0379(9) Uani 1 1 d . . . H11A H 1.5131 1.0419 0.6721 0.057 Uiso 1 1 calc R . . H11B H 1.4717 0.9747 0.7939 0.057 Uiso 1 1 calc R . . H11C H 1.3678 1.1699 0.6997 0.057 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 Br1 0.0388(2) 0.0689(3) 0.0453(2) 0.0151(3) 0.02630(16) 0.0041(3) O1 0.0334(14) 0.0292(12) 0.0212(12) 0.0026(10) 0.0085(11) 0.0020(11) C1 0.028(2) 0.043(2) 0.030(2) 0.0102(17) 0.0131(16) 0.0062(16) C2 0.043(2) 0.036(2) 0.0226(19) 0.0037(16) 0.0154(17) 0.0064(18) C3 0.035(2) 0.0293(19) 0.0255(18) -0.0001(14) 0.0090(16) -0.0008(15) C4 0.0249(18) 0.0230(17) 0.0221(18) 0.0036(14) 0.0087(14) 0.0029(14) C5 0.037(2) 0.038(3) 0.0295(19) -0.0071(15) 0.0154(16) -0.0066(16) C6 0.0308(17) 0.041(2) 0.0364(18) -0.001(3) 0.0145(14) -0.010(3) C7 0.0308(19) 0.0220(17) 0.0227(18) -0.0014(14) 0.0087(15) -0.0023(15) C8 0.0271(19) 0.0253(19) 0.0273(19) 0.0031(15) 0.0114(16) 0.0007(15) C9 0.0270(19) 0.031(2) 0.031(2) 0.0080(16) 0.0099(16) 0.0053(16) C10 0.037(2) 0.046(2) 0.044(3) -0.0046(19) 0.022(2) -0.0015(19) C11 0.0338(18) 0.036(2) 0.047(2) 0.005(2) 0.0153(16) -0.002(2) _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 Br1 C1 1.907(4) . ? O1 C7 1.433(4) . ? O1 H1O 0.8400 . ? C1 C2 1.372(6) . ? C1 C6 1.383(6) . ? C2 C3 1.395(5) . ? C2 H2 0.9500 . ? C3 C4 1.384(5) . ? C3 H3 0.9500 . ? C4 C5 1.396(5) . ? C4 C7 1.513(5) . ? C5 C6 1.389(5) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 C8 1.534(5) . ? C7 H7 1.0000 . ? C8 C9 1.511(5) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 C10 1.320(5) . ? C9 C11 1.508(6) . ? C10 H10A 0.9500 . ? C10 H10B 0.9500 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? 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 C7 O1 H1O 109.5 . . ? C2 C1 C6 121.8(4) . . ? C2 C1 Br1 119.7(3) . . ? C6 C1 Br1 118.5(3) . . ? C1 C2 C3 119.0(3) . . ? C1 C2 H2 120.5 . . ? C3 C2 H2 120.5 . . ? C4 C3 C2 121.0(4) . . ? C4 C3 H3 119.5 . . ? C2 C3 H3 119.5 . . ? C3 C4 C5 118.5(3) . . ? C3 C4 C7 119.9(3) . . ? C5 C4 C7 121.5(3) . . ? C6 C5 C4 121.2(4) . . ? C6 C5 H5 119.4 . . ? C4 C5 H5 119.4 . . ? C1 C6 C5 118.5(5) . . ? C1 C6 H6 120.7 . . ? C5 C6 H6 120.7 . . ? O1 C7 C4 111.9(3) . . ? O1 C7 C8 110.5(3) . . ? C4 C7 C8 111.3(3) . . ? O1 C7 H7 107.6 . . ? C4 C7 H7 107.6 . . ? C8 C7 H7 107.6 . . ? C9 C8 C7 113.6(3) . . ? C9 C8 H8A 108.9 . . ? C7 C8 H8A 108.9 . . ? C9 C8 H8B 108.9 . . ? C7 C8 H8B 108.9 . . ? H8A C8 H8B 107.7 . . ? C10 C9 C11 122.1(4) . . ? C10 C9 C8 121.8(4) . . ? C11 C9 C8 116.1(3) . . ? C9 C10 H10A 120.0 . . ? C9 C10 H10B 120.0 . . ? H10A C10 H10B 120.0 . . ? C9 C11 H11A 109.5 . . ? C9 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C9 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 C1 C2 C3 -1.6(6) . . . . ? Br1 C1 C2 C3 178.4(3) . . . . ? C1 C2 C3 C4 0.4(6) . . . . ? C2 C3 C4 C5 1.1(6) . . . . ? C2 C3 C4 C7 -177.3(3) . . . . ? C3 C4 C5 C6 -1.7(6) . . . . ? C7 C4 C5 C6 176.7(4) . . . . ? C2 C1 C6 C5 1.0(7) . . . . ? Br1 C1 C6 C5 -179.0(3) . . . . ? C4 C5 C6 C1 0.6(6) . . . . ? C3 C4 C7 O1 -134.9(3) . . . . ? C5 C4 C7 O1 46.8(4) . . . . ? C3 C4 C7 C8 101.0(4) . . . . ? C5 C4 C7 C8 -77.4(4) . . . . ? O1 C7 C8 C9 60.5(4) . . . . ? C4 C7 C8 C9 -174.5(3) . . . . ? C7 C8 C9 C10 -106.4(4) . . . . ? C7 C8 C9 C11 72.7(4) . . . . ? 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 O1 H1O O1 0.84 1.96 2.803(4) 178 2_746 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 30.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.488 _refine_diff_density_min -0.592 _refine_diff_density_rms 0.093