# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Paul Knochel' _publ_contact_author_address ; Department Chemie und Biochemie Ludwig-Maximilians-Universitat Munchen Butenandtstr. 5-13 Haus F Munchen D-81377 GERMANY ; _publ_contact_author_email KNOCH@CUP.UNI-MUENCHEN.DE _publ_section_title ; Preparation of silyl substituted crotylzinc reagents and their highly diastereoselective addition to carbonyl compounds ; loop_ _publ_author_name 'Paul Knochel' 'Peter Mayer' # Attachment 'ln291.cif' data_ln291 _database_code_depnum_ccdc_archive 'CCDC 673535' _audit_update_record 09-Jan-07 _chemical_name_common ?=20 _chemical_compound_source ? _exptl_crystal_description block #?# e.g.: needle, = platelet; pr _exptl_crystal_colour colourless _exptl_crystal_size_max 0.22 #?# in millimeters _exptl_crystal_size_mid 0.21 #?# in millimeters _exptl_crystal_size_min 0.20 #?# in millimeters _exptl_crystal_density_method 'not measured' _exptl_crystal_density_meas ? _exptl_special_details ? _audit_author_name 'Mayer, P.' #?# X-ray = operator _audit_creation_date 14-Jun-07 #?# style: = 18-Aug-1998 _diffrn_ambient_temperature 200(2) #?# in K _diffrn_source_type 'FR 591 generator' _diffrn_source_power 3.025 #?# in kW _diffrn_source_voltage 55.00 #?# in kV _diffrn_source_current 55.00 #?# in mA _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator 'MONTEL, graded multilayered X-ray = optics' _diffrn_radiation_collimation 0.20 _diffrn_measurement_device '95mm CCD camera on \k-goniostat' _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method ;CCD rotation images; thick slices, = omega-scan ; _diffrn_detector_area_resol_mean 9 _diffrn_special_details ? _diffrn_orient_matrix_type 'by Bruker AXS Collect from scalepack cell' _diffrn_orient_matrix_UB_11 0.1524590 _diffrn_orient_matrix_UB_12 0.0646818 _diffrn_orient_matrix_UB_13 0.0048504 _diffrn_orient_matrix_UB_21 0.0225286 _diffrn_orient_matrix_UB_22 -0.0182668 _diffrn_orient_matrix_UB_23 0.0627295 _diffrn_orient_matrix_UB_31 0.0060726 _diffrn_orient_matrix_UB_32 -0.1204712 _diffrn_orient_matrix_UB_33 -0.0235585 loop_ _reflns_scale_group_code _reflns_scale_meas_F 1 1.0 _cell_length_a 7.1579(2) _cell_length_b 8.0414(2) _cell_length_c 15.3538(3) _cell_angle_alpha 98.8045(14) _cell_angle_beta 96.7877(14) _cell_angle_gamma 112.5813(14) _cell_volume 791.08(3) _cell_measurement_temperature 200(2) #?# in K _cell_measurement_reflns_used 13684 _cell_measurement_theta_min 3.134 _cell_measurement_theta_max 27.485 _cell_special_details ? loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist -1 0 0 0.100000 1 0 0 0.100000 0 1 0 0.090000 0 -1 0 0.100000 0 1 -6 0.077000 0 0 1 0.099000 -1 9 18 0.088000 1 -9 13 0.105000 1 -9 -16 0.114000 -1 9 -14 0.102000 -7 8 -5 0.123000 3 -3 2 0.121000 3 -2 -5 0.115000 _exptl_absorpt_coefficient_mu 0.152 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _diffrn_reflns_number 6833 #xl _diffrn_reflns_av_R_equivalents 0.0200 #xl _diffrn_reflns_av_sigmaI/netI 0.0266 #xl _diffrn_reflns_limit_h_min -9 #xl _diffrn_reflns_limit_h_max 9 #xl _diffrn_reflns_limit_k_min -10 #xl _diffrn_reflns_limit_k_max 10 #xl _diffrn_reflns_limit_l_min -19 #xl _diffrn_reflns_limit_l_max 19 #xl _diffrn_reflns_theta_min 3.14 #xl _diffrn_reflns_theta_max 27.51 #xl _diffrn_measured_fraction_theta_max 0.991 #xl _diffrn_reflns_theta_full 27.51 #xl _diffrn_measured_fraction_theta_full 0.991 #xl _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' 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' N N 0.0061 0.0033 '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' Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _reflns_number_total 3610 #xl _reflns_number_gt 3171 #xl _reflns_threshold_expression >2sigma(I) #xl _reflns_special_details ? _refine_ls_structure_factor_coef Fsqd #xl _refine_ls_matrix_type full #xl _refine_ls_weighting_scheme calc #xl _refine_ls_weighting_details ;calc w=3D1/[\s^2^(Fo^2^)+(0.0440P)^2^+0.2222P] where = P=3D(Fo^2^+2Fc^2^)/3 ; #xl _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment refall #?# mixed --> = _refine_special_details ? _refine_ls_extinction_method none #xl _refine_ls_extinction_coef ? #xl _refine_ls_abs_structure_details ? #xl _refine_ls_abs_structure_Flack ? #xl _refine_ls_number_reflns 3610 #xl _refine_ls_number_parameters 256 #xl _refine_ls_number_restraints 0 #xl _refine_ls_R_factor_all 0.0439 #xl _refine_ls_R_factor_gt 0.0380 #xl _refine_ls_wR_factor_ref 0.1033 #xl _refine_ls_wR_factor_gt 0.0990 #xl _refine_ls_goodness_of_fit_ref 1.046 #xl _refine_ls_restrained_S_all 1.046 #xl _refine_ls_shift/su_max 0.001 #xl _refine_ls_shift/su_mean 0.000 #xl _refine_diff_density_max 0.226 #xl _refine_diff_density_min -0.205 #xl _refine_diff_density_rms 0.033 #xl _computing_data_collection 'Collect (Bruker AXS BV, 1997-2004)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (Otwinowski & Minor = 1997)' _computing_structure_solution ; A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C. Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna: SIR97: a new = tool for crystal structure determination and refinement; J. Appl. Crystallogr. = 1999, 32, 115-119. ; _computing_structure_refinement 'SHELXL-97 (G. M. Sheldrick. University of G\"ottingen, 97-2 version)' _computing_molecular_graphics ? _computing_publication_material ? 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 Si Si -0.38862(6) 0.17859(5) 0.84244(2) 0.04033(13) Uani 1 1 d . . . O1 O 0.09049(15) 0.60808(14) 0.67008(8) 0.0486(3) Uani 1 1 d . . . O2 O -0.98382(15) 0.18815(16) 0.46096(7) 0.0522(3) Uani 1 1 d . . . O3 O -0.82525(19) 0.05513(18) 0.38615(8) 0.0667(3) Uani 1 1 d . . . N N -0.82920(17) 0.16105(16) 0.45121(8) 0.0430(3) Uani 1 1 d . . . C1 C -0.2240(2) 0.42316(17) 0.84032(8) 0.0377(3) Uani 1 1 d . . . C2 C -0.0560(2) 0.45913(18) 0.78390(9) 0.0388(3) Uani 1 1 d . . . C3 C -0.08318(19) 0.56893(17) 0.71342(9) 0.0380(3) Uani 1 1 d . . . C4 C -0.28255(19) 0.46194(16) 0.64506(8) 0.0337(3) Uani 1 1 d . . . C5 C -0.4599(2) 0.49038(18) 0.65324(9) 0.0371(3) Uani 1 1 d . . . C6 C -0.6418(2) 0.38966(18) 0.59098(9) 0.0379(3) Uani 1 1 d . . . C7 C -0.64111(19) 0.26242(17) 0.51981(8) 0.0353(3) Uani 1 1 d . . . C8 C -0.4673(2) 0.23161(18) 0.50899(9) 0.0384(3) Uani 1 1 d . . . C9 C -0.2885(2) 0.33137(18) 0.57239(9) 0.0374(3) Uani 1 1 d . . . C10 C -0.2454(3) 0.5628(2) 0.89008(11) 0.0563(4) Uani 1 1 d . . . C11 C 0.1591(3) 0.5570(3) 0.84431(14) 0.0619(5) Uani 1 1 d . . . C12 C -0.5636(3) 0.1714(3) 0.92371(14) 0.0635(5) Uani 1 1 d . . . C13 C -0.2144(4) 0.0684(3) 0.8779(2) 0.0728(6) Uani 1 1 d . . . C14 C -0.5401(4) 0.0520(3) 0.72904(12) 0.0710(6) Uani 1 1 d . . . H3 H -0.086(2) 0.684(2) 0.7433(10) 0.037(4) Uiso 1 1 d . . . H5 H -0.458(2) 0.581(2) 0.7040(11) 0.046(4) Uiso 1 1 d . . . H2 H -0.067(2) 0.340(2) 0.7492(10) 0.042(4) Uiso 1 1 d . . . H9 H -0.170(2) 0.309(2) 0.5655(11) 0.045(4) Uiso 1 1 d . . . H8 H -0.472(3) 0.143(2) 0.4587(12) 0.050(4) Uiso 1 1 d . . . H101 H -0.156(3) 0.692(3) 0.8900(13) 0.067(5) Uiso 1 1 d . . . H7 H -0.759(3) 0.408(2) 0.5960(11) 0.048(4) Uiso 1 1 d . . . H121 H -0.655(4) 0.223(3) 0.9025(17) 0.097(8) Uiso 1 1 d . . . H102 H -0.349(3) 0.539(3) 0.9252(14) 0.069(6) Uiso 1 1 d . . . H111 H 0.169(3) 0.483(3) 0.8894(15) 0.079(6) Uiso 1 1 d . . . H1 H 0.080(3) 0.677(3) 0.6336(15) 0.075(6) Uiso 1 1 d . . . H131 H -0.299(4) -0.059(4) 0.8787(18) 0.109(8) Uiso 1 1 d . . . H122 H -0.655(4) 0.041(4) 0.9261(18) 0.108(8) Uiso 1 1 d . . . H141 H -0.614(4) -0.080(3) 0.7293(15) 0.089(7) Uiso 1 1 d . . . H112 H 0.169(3) 0.684(3) 0.8744(14) 0.074(6) Uiso 1 1 d . . . H132 H -0.128(4) 0.070(3) 0.8375(16) 0.083(7) Uiso 1 1 d . . . H142 H -0.454(4) 0.063(4) 0.6839(19) 0.108(9) Uiso 1 1 d . . . H143 H -0.646(3) 0.092(3) 0.7184(15) 0.074(7) Uiso 1 1 d . . . H113 H 0.268(4) 0.562(3) 0.8086(16) 0.086(7) Uiso 1 1 d . . . H123 H -0.490(4) 0.239(4) 0.9844(19) 0.105(8) Uiso 1 1 d . . . H133 H -0.128(5) 0.134(5) 0.936(2) 0.144(13) Uiso 1 1 d . . . 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 Si 0.0485(2) 0.0360(2) 0.0343(2) 0.00820(14) 0.00838(15) 0.01474(16) O1 0.0329(5) 0.0460(6) 0.0635(7) 0.0226(5) 0.0075(4) 0.0090(4) O2 0.0332(5) 0.0656(7) 0.0523(6) 0.0182(5) 0.0021(4) 0.0141(5) O3 0.0561(7) 0.0741(8) 0.0498(7) -0.0101(6) -0.0058(5) 0.0185(6) N 0.0368(6) 0.0451(6) 0.0397(6) 0.0154(5) 0.0022(5) 0.0083(5) C1 0.0437(7) 0.0349(6) 0.0309(6) 0.0035(5) -0.0028(5) 0.0166(5) C2 0.0367(7) 0.0329(6) 0.0430(7) 0.0084(5) -0.0015(5) 0.0128(5) C3 0.0330(6) 0.0305(6) 0.0455(7) 0.0094(5) 0.0013(5) 0.0092(5) C4 0.0332(6) 0.0301(6) 0.0370(6) 0.0126(5) 0.0041(5) 0.0109(5) C5 0.0385(7) 0.0365(6) 0.0372(6) 0.0089(5) 0.0059(5) 0.0161(5) C6 0.0330(6) 0.0428(7) 0.0412(7) 0.0152(5) 0.0080(5) 0.0166(5) C7 0.0323(6) 0.0359(6) 0.0342(6) 0.0139(5) 0.0031(5) 0.0089(5) C8 0.0407(7) 0.0379(6) 0.0356(6) 0.0085(5) 0.0076(5) 0.0147(5) C9 0.0338(6) 0.0396(6) 0.0409(7) 0.0114(5) 0.0071(5) 0.0163(5) C10 0.0786(12) 0.0441(8) 0.0467(8) 0.0027(6) 0.0082(8) 0.0293(8) C11 0.0437(9) 0.0652(11) 0.0652(11) 0.0205(9) -0.0116(8) 0.0139(8) C12 0.0658(11) 0.0709(12) 0.0567(11) 0.0172(9) 0.0231(9) 0.0264(10) C13 0.0830(14) 0.0634(12) 0.0985(17) 0.0427(12) 0.0349(13) 0.0439(11) C14 0.0883(15) 0.0424(9) 0.0457(9) 0.0052(7) 0.0033(9) -0.0078(9) 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 Si C14 1.8457(18) . ? Si C12 1.8615(19) . ? Si C13 1.864(2) . ? Si C1 1.8725(14) . ? O1 C3 1.4305(17) . ? O1 H1 0.86(2) . ? O2 N 1.2285(16) . ? O3 N 1.2201(17) . ? N C7 1.4648(16) . ? C1 C10 1.329(2) . ? C1 C2 1.529(2) . ? C2 C11 1.536(2) . ? C2 C3 1.5372(18) . ? C2 H2 0.992(16) . ? C3 C4 1.5183(17) . ? C3 H3 0.973(15) . ? C4 C5 1.3895(18) . ? C4 C9 1.3946(18) . ? C5 C6 1.3872(19) . ? C5 H5 0.977(16) . ? C6 C7 1.3798(19) . ? C6 H7 0.911(17) . ? C7 C8 1.3821(19) . ? C8 C9 1.3808(19) . ? C8 H8 0.954(17) . ? C9 H9 0.948(16) . ? C10 H101 0.99(2) . ? C10 H102 0.95(2) . ? C11 H111 0.99(2) . ? C11 H112 1.03(2) . ? C11 H113 1.00(2) . ? C12 H121 0.95(3) . ? C12 H122 1.01(3) . ? C12 H123 0.98(3) . ? C13 H131 0.97(3) . ? C13 H132 0.92(2) . ? C13 H133 0.96(4) . ? C14 H141 0.98(2) . ? C14 H142 0.97(3) . ? C14 H143 0.94(2) . ? 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 C14 Si C12 110.23(11) . . ? C14 Si C13 108.72(13) . . ? C12 Si C13 109.52(11) . . ? C14 Si C1 110.07(7) . . ? C12 Si C1 110.36(8) . . ? C13 Si C1 107.89(9) . . ? C3 O1 H1 106.7(14) . . ? O3 N O2 122.67(12) . . ? O3 N C7 118.75(12) . . ? O2 N C7 118.58(12) . . ? C10 C1 C2 120.53(14) . . ? C10 C1 Si 120.96(13) . . ? C2 C1 Si 118.42(9) . . ? C1 C2 C11 110.72(13) . . ? C1 C2 C3 111.77(11) . . ? C11 C2 C3 111.05(12) . . ? C1 C2 H2 109.4(9) . . ? C11 C2 H2 108.3(9) . . ? C3 C2 H2 105.5(9) . . ? O1 C3 C4 110.44(11) . . ? O1 C3 C2 107.03(11) . . ? C4 C3 C2 111.78(10) . . ? O1 C3 H3 109.9(9) . . ? C4 C3 H3 108.3(9) . . ? C2 C3 H3 109.4(9) . . ? C5 C4 C9 119.08(12) . . ? C5 C4 C3 121.61(12) . . ? C9 C4 C3 119.31(11) . . ? C6 C5 C4 120.98(12) . . ? C6 C5 H5 119.1(9) . . ? C4 C5 H5 119.9(9) . . ? C7 C6 C5 118.18(12) . . ? C7 C6 H7 120.4(11) . . ? C5 C6 H7 121.4(11) . . ? C6 C7 C8 122.47(12) . . ? C6 C7 N 118.89(12) . . ? C8 C7 N 118.60(12) . . ? C9 C8 C7 118.46(12) . . ? C9 C8 H8 121.1(10) . . ? C7 C8 H8 120.4(10) . . ? C8 C9 C4 120.82(12) . . ? C8 C9 H9 118.6(10) . . ? C4 C9 H9 120.6(10) . . ? C1 C10 H101 120.9(11) . . ? C1 C10 H102 120.0(13) . . ? H101 C10 H102 119.1(16) . . ? C2 C11 H111 108.3(13) . . ? C2 C11 H112 105.7(12) . . ? H111 C11 H112 111.4(17) . . ? C2 C11 H113 110.7(14) . . ? H111 C11 H113 106.8(18) . . ? H112 C11 H113 113.9(18) . . ? Si C12 H121 107.7(15) . . ? Si C12 H122 112.0(15) . . ? H121 C12 H122 106(2) . . ? Si C12 H123 112.9(15) . . ? H121 C12 H123 110(2) . . ? H122 C12 H123 109(2) . . ? Si C13 H131 108.5(16) . . ? Si C13 H132 110.1(14) . . ? H131 C13 H132 109(2) . . ? Si C13 H133 111(2) . . ? H131 C13 H133 111(3) . . ? H132 C13 H133 107(2) . . ? Si C14 H141 109.4(13) . . ? Si C14 H142 112.2(16) . . ? H141 C14 H142 109(2) . . ? Si C14 H143 106.7(14) . . ? H141 C14 H143 104.0(19) . . ? H142 C14 H143 115(2) . . ? 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 C14 Si C1 C10 119.83(16) . . . . ? C12 Si C1 C10 -2.06(16) . . . . ? C13 Si C1 C10 -121.68(15) . . . . ? C14 Si C1 C2 -63.50(14) . . . . ? C12 Si C1 C2 174.61(11) . . . . ? C13 Si C1 C2 54.99(13) . . . . ? C10 C1 C2 C11 63.53(18) . . . . ? Si C1 C2 C11 -113.15(12) . . . . ? C10 C1 C2 C3 -60.84(17) . . . . ? Si C1 C2 C3 122.47(10) . . . . ? C1 C2 C3 O1 175.18(10) . . . . ? C11 C2 C3 O1 50.99(16) . . . . ? C1 C2 C3 C4 -63.78(14) . . . . ? C11 C2 C3 C4 172.03(14) . . . . ? O1 C3 C4 C5 -143.94(12) . . . . ? C2 C3 C4 C5 97.01(14) . . . . ? O1 C3 C4 C9 36.29(15) . . . . ? C2 C3 C4 C9 -82.75(15) . . . . ? C9 C4 C5 C6 0.73(19) . . . . ? C3 C4 C5 C6 -179.04(11) . . . . ? C4 C5 C6 C7 -1.03(19) . . . . ? C5 C6 C7 C8 0.41(19) . . . . ? C5 C6 C7 N -177.19(11) . . . . ? O3 N C7 C6 176.54(13) . . . . ? O2 N C7 C6 -2.48(18) . . . . ? O3 N C7 C8 -1.15(19) . . . . ? O2 N C7 C8 179.83(12) . . . . ? C6 C7 C8 C9 0.50(19) . . . . ? N C7 C8 C9 178.11(11) . . . . ? C7 C8 C9 C4 -0.82(19) . . . . ? C5 C4 C9 C8 0.22(19) . . . . ? C3 C4 C9 C8 179.99(11) . . . . ? loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag ? ? ? ? ? ? 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 _geom_hbond_publ_flag ? ? ? ? ? ? ? ? ? _geom_special_details ? _audit_block_code SiC14H21NO3_ln291_knochel=20 _audit_creation_method 'form98_non/compatible with = shelxl97-2' _chemical_name_systematic ? _chemical_formula_moiety 'C14 H21 N O3 Si' _chemical_formula_sum 'C14 H21 N O3 Si' _chemical_formula_weight 279.407 _chemical_melting_point ? #?# in K! _cell_formula_units_Z 2 #?# adjust to _chemical_formula_[] _exptl_crystal_density_diffrn 1.17301(4) _exptl_crystal_F_000 300