Copper-catalyzed asymmetric hydrogenation of 2-substituted ketones <i>via</i> dynamic kinetic resolution.
Zatolochnaya, Olga V.; Rodríguez, Sonia; Zhang, Yongda; Lao, Kendricks S.; Tcyrulnikov, Sergei; Li, Guisheng; Wang, Xiao-Jun; Qu, Bo; Biswas, Soumik; Mangunuru, Hari P. R.; Rivalti, Daniel; Sieber, Joshua D.; Desrosiers, Jean-Nicolas; Leung, Joyce C.; Grinberg, Nelu; Lee, Heewon; Haddad, Nizar; Yee, Nathan K.; Song, Jinhua J.; Kozlowski, Marisa C.; Senanayake, Chris H.; Chemical science 9 (2018) 4505–4510; doi:10.1039/c8sc00434j

data_1549274
_publ_section_title
;
 Copper-catalyzed asymmetric hydrogenation of 2-substituted ketones
 <i>via</i> dynamic kinetic resolution.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              4505
_journal_page_last               4510
_journal_paper_doi               10.1039/c8sc00434j
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C64 H92 Cl2 Cu2 N4 O4 P4'
_chemical_formula_sum            'C64 H92 Cl2 Cu2 N4 O4 P4'
_chemical_formula_weight         1303.27
_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
_audit_creation_date             2018-01-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5289)
;
_audit_update_record
;
2018-01-12 deposited with the CCDC.
2018-04-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6900(7)
_cell_length_b                   16.8264(8)
_cell_length_c                   30.4315(14)
_cell_measurement_reflns_used    9987
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.645
_cell_measurement_theta_min      2.904
_cell_volume                     7010.0(6)
_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  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.99
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0385
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            32805
_diffrn_reflns_point_group_measured_fraction_full 0.945
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        66.680
_diffrn_reflns_theta_max         66.680
_diffrn_reflns_theta_min         2.904
_exptl_absorpt_coefficient_mu    2.663
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9003
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0739 before and 0.0477 after correction.
The Ratio of minimum to maximum transmission is 0.9003.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.235
_exptl_crystal_description       plate
_exptl_crystal_F_000             2752
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.519
_refine_diff_density_min         -0.477
_refine_diff_density_rms         0.120
_refine_ls_abs_structure_details
;
 Flack x determined using 4168 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.041(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     745
_refine_ls_number_reflns         11727
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0350
_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^)+(0.0767P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1064
_refine_ls_wR_factor_ref         0.1105
_reflns_Friedel_coverage         0.757
_reflns_Friedel_fraction_full    0.906
_reflns_Friedel_fraction_max     0.906
_reflns_number_gt                10544
_reflns_number_total             11727
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc00434j2.cif
_cod_data_source_block           scan_0m_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1549273--1549274.cif.'
_cod_database_code               1549274
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.901
_olex2_refinement_description
;
1. 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
2.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C18(H18A,H18B), C44(H44A,H44B), C60(H60A,H60B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C25(H25), C26(H26), C27(H27), C35(H35),
 C36(H36), C37(H37), C40(H40), C41(H41), C42(H42)
2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C52(H52A,
 H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C57(H57A,H57B,H57C),
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C62(H62A,H62B,H62C), C63(H63A,H63B,
 H63C), C64(H64A,H64B,H64C)
;
_olex2_submission_special_instructions 'No special instructions were received'