RuPHOX-Ru Catalyzed Asymmetric Hydrogenation of α-Substituted Tetralones via a Dynamic Kinetic Resolution
Li, Jingjing; Ye, Jianxun; Zhou, Jiayu; Li, Jing; Liu, Delong; Zhang, Wanbin; Chemical Communications  (2022) –; doi:10.1039/D2CC01193J

data_7129887
_publ_section_title
;
 RuPHOX-Ru Catalyzed Asymmetric Hydrogenation of \a-Substituted Tetralones
 via a Dynamic Kinetic Resolution
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01193J
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H17 Cl O2'
_chemical_formula_sum            'C17 H17 Cl O2'
_chemical_formula_weight         288.75
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-03 deposited with the CCDC.	2022-03-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   12.7413(4)
_cell_length_b                   12.7413(4)
_cell_length_c                   37.1305(16)
_cell_measurement_reflns_used    9805
_cell_measurement_temperature    173.0
_cell_measurement_theta_max      65.74
_cell_measurement_theta_min      4.21
_cell_volume                     6027.8(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      173.0
_diffrn_measured_fraction_theta_full 0.997
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0659
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            50566
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.783
_diffrn_reflns_theta_max         66.783
_diffrn_reflns_theta_min         3.668
_diffrn_source_current           40.0
_diffrn_source_power             1.8
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.226
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6241
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1318 before and 0.0893 after correction.
The Ratio of minimum to maximum transmission is 0.8290.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_description       plate
_exptl_crystal_F_000             2432
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.304
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1609 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.053(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     383
_refine_ls_number_reflns         5332
_refine_ls_number_restraints     230
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0790
_refine_ls_R_factor_gt           0.0706
_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^)+(0.0970P)^2^+2.2265P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2007
_refine_ls_wR_factor_ref         0.2100
_reflns_Friedel_coverage         0.698
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                4551
_reflns_number_total             5332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01193j2.cif
_cod_data_source_block           b_a
_cod_original_cell_volume        6027.8(5)
_cod_database_code               7129887
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.808
_shelx_estimated_absorpt_t_min   0.664
_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, All O(H) groups
2. Restrained distances
 C2-C3 = C5-C6 = C6-C7
 1.37 with sigma of 0.02
 C2-C7
 1.38 with sigma of 0.02
 C3-C4 = C4-C5
 1.36 with sigma of 0.02
 C2-C6
 2.38 with sigma of 0.04
 C3-C5
 2.36 with sigma of 0.04
 C2-C4 = C4-C6 = C5-C7
 2.37 with sigma of 0.04
 C2-C3 \\sim C3-C4 \\sim C4-C5 \\sim C5-C6 \\sim C6-C7 \\sim C7-C2
 with sigma of 0.02
 C2-C6 \\sim C2-C4 \\sim C6-C4 \\sim C5-C3 \\sim C5-C7 \\sim C7-C3
 with sigma of 0.04
 C2-C1 \\sim C2-C1A
 with sigma of 0.04
 C2-O1 \\sim C2-O1A
 with sigma of 0.02
 O1-C1 \\sim O1A-C1A
 with sigma of 0.02
 O1-C2 \\sim O1A-C2
 with sigma of 0.02
 O1A-C1A \\sim O1-C1
 with sigma of 0.02
3. Restrained planarity
 C2, C3, C4, C5, C6, C7
 with sigma of 0.1
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
6. Rigid body (RIGU) restrains
 C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(O1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(O1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(1)
8.a Ternary CH refined with riding coordinates:
 C25(H25), C26(H26), C8(H8), C9(H9)
8.b Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C10(H10A,H10B), C28(H28A,H28B), C11(H11A,H11B)
8.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C31(H31), C34(H34), C24(H24), C33(H33), C17(H17), C16(H16),
 C13(H13), C20(H20), C21(H21), C14(H14), C3(H3), C6(H6), C7(H7)
8.d Tetrahedral OH refined with riding coordinates:
 O4(H4), O2(H2)
8.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C1(H1A,H1B,H1C), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              19457
_olex2_submission_special_instructions 'No special instructions were received'