Highly efficient synthesis of enantioenriched vicinal halohydrins <i>via</i> Ir-catalyzed asymmetric hydrogenation using dynamic kinetic resolution.
He, Bin; Chen, Gen-Qiang; Zhang, Xumu; Chemical communications (Cambridge, England) 60 (2024) 9785–9788; doi:10.1039/d4cc02529f

data_7133456
_publ_section_title
;
 Highly efficient synthesis of enantioenriched vicinal halohydrins
 <i>via</i> Ir-catalyzed asymmetric hydrogenation using dynamic kinetic
 resolution.
;
_journal_issue                   72
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9785
_journal_page_last               9788
_journal_paper_doi               10.1039/d4cc02529f
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C9 H8 Cl2 O2'
_chemical_formula_sum            'C9 H8 Cl2 O2'
_chemical_formula_weight         219.05
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-24
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-05-26 deposited with the CCDC.	2024-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.291(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7032(9)
_cell_length_b                   4.8645(5)
_cell_length_c                   11.7272(12)
_cell_measurement_reflns_used    8633
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.21
_cell_measurement_theta_min      4.02
_cell_volume                     465.68(8)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON II area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0549
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            7937
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.281
_diffrn_reflns_theta_min         4.019
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.11
_diffrn_source_power             0.05550000000000001
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.971
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.3653
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1429 before and 0.0913 after correction.
The Ratio of minimum to maximum transmission is 0.4847.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       block
_exptl_crystal_F_000             224
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.24
_refine_diff_density_max         1.023
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Flack x determined using 766 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.172
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     159
_refine_ls_number_reflns         1806
_refine_ls_number_restraints     35
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0552
_refine_ls_R_factor_gt           0.0550
_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^)+(0.0233P)^2^+1.6071P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1327
_refine_ls_wR_factor_ref         0.1328
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                1803
_reflns_number_total             1806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02529f2.cif
_cod_data_source_block           cxy3548_0m
_cod_depositor_comments
'Adding full bibliography for 7133455--7133456.cif.'
_cod_database_code               7133456
_shelx_shelxl_version_number     2019/2
_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 O(H) groups
2. Restrained distances
 C2-C7 \\sim C2A-C7A
 with sigma of 0.04
 O2-C8 \\sim O2A-C8A
 with sigma of 0.04
 C2-C8 \\sim C2A-C8A
 with sigma of 0.02
 C4-C7 \\sim C4A-C7A
 with sigma of 0.04
 O2-C9 \\sim O2A-C9A
 with sigma of 0.02
 O2-C6 \\sim O2A-C6A
 with sigma of 0.04
 C5-C8 \\sim C5A-C8A
 with sigma of 0.04
 C5-C7 \\sim C5A-C7A
 with sigma of 0.02
 C7-C8 \\sim C7A-C8A
 with sigma of 0.02
 C8-C9 \\sim C8A-C9A
 with sigma of 0.02
 C3-C8 \\sim C3A-C8A
 with sigma of 0.04
 C6-C8 \\sim C6A-C8A
 with sigma of 0.04
 Cl1-C7 \\sim Cl1A-C7A
 with sigma of 0.04
 C7-C9 \\sim C7A-C9A
 with sigma of 0.04
 O1-C8 \\sim O1A-C8A
 with sigma of 0.04
 O1-C2 \\sim O1A-C2A
 with sigma of 0.02
 O1-C1 \\sim O1A-C1A
 with sigma of 0.02
 Cl2-C6 \\sim Cl2A-C6A
 with sigma of 0.02
 Cl1-C5 \\sim Cl1A-C5A
 with sigma of 0.02
 C2-C3 \\sim C2A-C3A
 with sigma of 0.02
 C1-C6 \\sim C1A-C6A
 with sigma of 0.02
 Cl1-C4 \\sim Cl1A-C4A
 with sigma of 0.04
 C3-C4 \\sim C3A-C4A
 with sigma of 0.02
 Cl2-C1 \\sim Cl2A-C1A
 with sigma of 0.04
 Cl2-C9 \\sim Cl2A-C9A
 with sigma of 0.04
 C4-C5 \\sim C4A-C5A
 with sigma of 0.02
 O1-C3 \\sim O1A-C3A
 with sigma of 0.04
 O1-C6 \\sim O1A-C6A
 with sigma of 0.04
 C1-C2 \\sim C1A-C2A
 with sigma of 0.04
 C1-C9 \\sim C1A-C9A
 with sigma of 0.04
 C6-C9 \\sim C6A-C9A
 with sigma of 0.02
 C2-C4 \\sim C2A-C4A
 with sigma of 0.04
 C2-C9 \\sim C2A-C9A
 with sigma of 0.04
 C3-C5 \\sim C3A-C5A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O2A) = Uanis(O2)
Uanis(C5) = Uanis(C5A)
Uanis(C1A) = Uanis(C1)
Uanis(C3A) = Uanis(C3)
Uanis(C8) = Uanis(C8A)
Uanis(C6A) = Uanis(C6)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(C4) = Uanis(C4A)
Uanis(C2) = Uanis(C2A)
Uanis(C7) = Uanis(C7A)
Uanis(C9) = Uanis(C9A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(O1) = Uanis(O1A)
4. Others
 Sof(C8A)=Sof(Cl1A)=Sof(C5A)=Sof(C4A)=Sof(H4A)=Sof(C7A)=Sof(H7A)=Sof(C3A)=
 Sof(H3A)=Sof(C2A)=Sof(C9A)=Sof(H9A)=Sof(O1A)=Sof(O2A)=Sof(H2A)=Sof(C6A)=
 Sof(H6A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(Cl2A)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(O1)=Sof(O2)=Sof(H2)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=
 Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=
 Sof(C8)=Sof(C9)=Sof(H9)=FVAR(1)
5.a Riding coordinates:
 O2A(H2A)
5.b Ternary CH refined with riding coordinates:
 C6(H6), C9(H9), C9A(H9A), C6A(H6A)
5.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
5.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7(H7), C4A(H4A), C7A(H7A), C3A(H3A)
5.e Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              54878
_shelx_hkl_checksum              36889
_olex2_submission_special_instructions 'No special instructions were received'