A Bulky Chiral N-Heterocyclic Carbene Palladium Catalyst Enables Highly Enantioselective Suzuki-Miyaura Cross-Coupling Reactions for the Synthesis of Biaryl Atropisomers.
Shen, Di; Xu, Youjun; Shi, Shi-Liang; Journal of the American Chemical Society 141 (2019) 14938–14945; doi:10.1021/jacs.9b08578

data_4127633
_publ_section_title
;
 A Bulky Chiral N-Heterocyclic Carbene Palladium Catalyst Enables Highly
 Enantioselective Suzuki-Miyaura Cross-Coupling Reactions for the
 Synthesis of Biaryl Atropisomers.
;
_journal_issue                   37
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14938
_journal_page_last               14945
_journal_paper_doi               10.1021/jacs.9b08578
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C58 H59 Cl N2 Pd'
_chemical_formula_sum            'C58 H59 Cl N2 Pd'
_chemical_formula_weight         925.92
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4332(4)
_cell_length_b                   19.3921(6)
_cell_length_c                   19.9589(6)
_cell_measurement_reflns_used    9976
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      54.61
_cell_measurement_theta_min      2.76
_cell_volume                     4812.2(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      169.96
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0748
_diffrn_reflns_av_unetI/netI     0.0937
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            31827
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.925
_diffrn_reflns_theta_min         2.764
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.597
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.6617
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1308 before and 0.0811 after correction. The Ratio of minimum to maximum transmission is 0.8813. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       block
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.042
_refine_diff_density_min         -0.653
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.042(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     566
_refine_ls_number_reflns         8841
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0942
_refine_ls_R_factor_gt           0.0599
_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^)+(0.0489P)^2^+4.9351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1162
_refine_ls_wR_factor_ref         0.1330
_reflns_Friedel_coverage         0.805
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                6459
_reflns_number_total             8841
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b08578_si_003.cif
_cod_data_source_block           mj19192_0m
_cod_database_code               4127633
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.881
_shelx_estimated_absorpt_t_min   0.781
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.958(19)
 0.042(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C19(H19), C28(H28), C42(H42), C51(H51)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C11(H11A,H11B), C12(H12A,H12B)
4.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C15(H15), C17(H17), C21(H21),
 C22(H22), C23(H23), C24(H24), C25(H25), C30(H30), C31(H31), C32(H32), C33(H33),
  C34(H34), C38(H38), C40(H40), C44(H44), C45(H45), C46(H46), C47(H47),
 C48(H48), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57)
4.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C35(H35A,H35B,H35C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              46998
_shelx_hkl_checksum              28277
_olex2_submission_special_instructions 'No special instructions were received'