Asymmetric C–H Activation for the Synthesis of P- and Axially Chiral Biaryl Phosphine Oxides by an Achiral Cp*Ir Catalyst with Chiral Carboxylic Amide
Zhang, Chao-Wei; Hu, Xian-Qi; Dai, Yuan-Hao; Yin, Peng; Wang, Chuanyong; Duan, Wei-Liang; ACS Catalysis  (2021) 193–199; doi:10.1021/acscatal.1c05080

data_4519230
_publ_section_title
;
 Asymmetric C--H Activation for the Synthesis of P- and Axially Chiral
 Biaryl Phosphine Oxides by an Achiral Cp*Ir Catalyst with Chiral
 Carboxylic Amide
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              193
_journal_page_last               199
_journal_paper_doi               10.1021/acscatal.1c05080
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C46 H39 O P, C4 H8 O'
_chemical_formula_sum            'C50 H47 O2 P'
_chemical_formula_weight         710.84
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-06 deposited with the CCDC.	2021-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   12.5608(8)
_cell_length_b                   12.5608(8)
_cell_length_c                   22.1603(16)
_cell_measurement_reflns_used    9960
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      27.46
_cell_measurement_theta_min      2.62
_cell_volume                     3027.9(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0627
_diffrn_reflns_av_unetI/netI     0.0819
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            28540
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.508
_diffrn_reflns_theta_min         2.086
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.107
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5625
_exptl_crystal_density_diffrn    1.170
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1134
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.445
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2155 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         9197
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1154
_refine_ls_R_factor_gt           0.0667
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0870P)^2^+0.1439P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1457
_refine_ls_wR_factor_ref         0.1659
_reflns_Friedel_coverage         0.983
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                6061
_reflns_number_total             9197
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05080_si_002.cif
_cod_data_source_block           1
_cod_original_cell_volume        3027.9(4)
_cod_database_code               4519230
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C1(H1)
1.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C5(H5A,H5B), C3(H3A,H3B), C4(H4A,H4B)
1.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C42(H42), C24(H24), C14(H14), C17(H17), C15(H15), C39(H39),
 C16(H16), C23(H23), C22(H22), C29(H29), C28(H28), C43(H43), C32(H32), C30(H30),
  C41(H41), C8(H8), C45(H45), C35(H35), C44(H44), C38(H38), C12(H12), C31(H31),
 C37(H37), C9(H9), C11(H11), C36(H36), C10(H10), C49(H49), C48(H48)
1.d Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C), C47(H47A,H47B,H47C)
;
_shelx_res_checksum              12484
_shelx_hkl_checksum              65721
_olex2_submission_special_instructions 'No special instructions were received'