Asymmetric addition of Grignard reagents to ketones: culmination of the ligand-mediated methodology allows modular construction of chiral tertiary alcohols
Monasterolo, Claudio; O'Gara, Ryan; Kavanagh, Saranna; Byrne, Sadbh Elise; Bieszczad, Bartosz; Murray, Orla; Wiesinger, Michael; Lynch, Rebecca; Nikitin, Kirill; Gilheany, Declan Gerard; Chemical Science  (2022) –; doi:10.1039/D1SC06350B

data_1566846
_publ_section_title
;
 Asymmetric addition of Grignard reagents to ketones: culmination of the
 ligand-mediated methodology allows modular construction of chiral
 tertiary alcohols
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC06350B
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H23 Br2 N O2'
_chemical_formula_sum            'C20 H23 Br2 N O2'
_chemical_formula_weight         469.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014
_audit_update_record
;
2022-03-15 deposited with the CCDC.	2022-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.2355(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.0842(2)
_cell_length_b                   18.1183(2)
_cell_length_c                   15.8577(2)
_cell_measurement_reflns_used    37827
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.6350
_cell_measurement_theta_min      3.4850
_cell_volume                     4091.96(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.3196
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0342
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            82455
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.941
_diffrn_reflns_theta_min         3.508
_diffrn_source                   'micro-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    5.121
_exptl_absorpt_correction_T_max  0.915
_exptl_absorpt_correction_T_min  0.575
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
; 
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015) 
Numerical absorption correction based on gaussian integration over 
a multifaceted crystal model 
Empirical absorption correction using spherical harmonics, 
implemented in SCALE3 ABSPACK scaling algorithm. 
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.523
_exptl_crystal_description       plate
_exptl_crystal_F_000             1888
_exptl_crystal_size_max          0.169
_exptl_crystal_size_mid          0.092
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.880
_refine_diff_density_min         -0.679
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
; 
 Flack x determined using 7534 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.043(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     909
_refine_ls_number_reflns         17120
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0276
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0330P)^2^+1.7390P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0669
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.927
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                16318
_reflns_number_total             17120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06350b2.cif
_cod_data_source_block           gil118
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               1566846
_shelxl_version_number           2014-3
_shelx_res_checksum              86421
_shelx_hkl_checksum              93455