Enantioselective Synthesis of α-Amidoboronates Catalyzed by Planar-Chiral NHC-Cu(I) Complexes.
Schwamb, C. Benjamin; Fitzpatrick, Keegan P.; Brueckner, Alexander C.; Richardson, H. Camille; Cheong, Paul H.-Y.; Scheidt, Karl A.; Journal of the American Chemical Society 140 (2018) 10644–10648; doi:10.1021/jacs.8b05045

data_4132597
_publ_section_title
;
 Enantioselective Synthesis of \a-Amidoboronates Catalyzed by
 Planar-Chiral NHC-Cu(I) Complexes.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10644
_journal_page_last               10648
_journal_paper_doi               10.1021/jacs.8b05045
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H34 Cl Cu Fe N2 O'
_chemical_formula_sum            'C34 H34 Cl Cu Fe N2 O'
_chemical_formula_weight         641.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           3
_space_group_name_Hall           'P 2y'
_space_group_name_H-M_alt        'P 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.359(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.3929(16)
_cell_length_b                   9.5949(8)
_cell_length_c                   18.9878(17)
_cell_measurement_reflns_used    2846
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      58.331
_cell_measurement_theta_min      2.341
_cell_volume                     3330.3(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      249.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0685
_diffrn_reflns_av_unetI/netI     0.0974
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22492
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        65.077
_diffrn_reflns_theta_max         65.077
_diffrn_reflns_theta_min         2.341
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    5.217
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6396
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0831 before and 0.0500 after correction. The Ratio of minimum to maximum transmission is 0.8496. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_description       needle
_exptl_crystal_F_000             1328
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.025
_exptl_crystal_size_min          0.014
_refine_diff_density_max         0.368
_refine_diff_density_min         -0.305
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1672 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.003(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.972
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     734
_refine_ls_number_reflns         11142
_refine_ls_number_restraints     889
_refine_ls_restrained_S_all      0.978
_refine_ls_R_factor_all          0.1340
_refine_ls_R_factor_gt           0.0691
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0902P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1630
_refine_ls_wR_factor_ref         0.2034
_reflns_Friedel_coverage         0.848
_reflns_Friedel_fraction_full    0.964
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                5769
_reflns_number_total             11142
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05045_si_002.cif
_cod_data_source_block           cx1054a
_cod_database_code               4132597
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.508
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3.a Me refined with riding coordinates:
 C9(H9A,H9B,H9C)
3.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C17(H17), C19(H19), C24(H24), C26(H26),
 C27(H27), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C12A(H12A),
 C13A(H13A), C14A(H14A), C17A(H17A), C19A(H19A), C24A(H24A), C26A(H26A),
 C27A(H27A), C30A(H30A), C31A(H31A), C32A(H32A), C33A(H33A), C34A(H34A)
3.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C),
 C21(H21A,H21B,H21C), C28(H28A,H28B,H28C), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,
 H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F),
 C21A(H21D,H21E,H21F), C28A(H28D,H28E,H28F)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.

Total solvent accessible volume / cell = 440.2 Ang^3^ [13.2%]
Total electron count / cell = 67.4
;
_shelx_res_checksum              75224
_shelx_hkl_checksum              27349
_shelx_fab_checksum              9059
_olex2_date_sample_data_collection 2017-08-28
_olex2_date_sample_submission    2017-08-18
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx1054a
_olex2_submission_special_instructions 'No special instructions were received'