Desymmetrization of cyclic 1,3-diketones via Ir-catalyzed hydrogenation: an efficient approach to cyclic hydroxy ketones with a chiral quaternary carbon
Gong, Quan; Wen, Jialin; Zhang, Xumu; Chemical Science  (2019) –; doi:10.1039/C9SC01769K

data_1551082
_publ_section_title
;
 Desymmetrization of cyclic 1,3-diketones via Ir-catalyzed hydrogenation:
 an efficient approach to cyclic hydroxy ketones with a chiral quaternary
 carbon
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01769K
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C13 H16 O2'
_chemical_formula_sum            'C13 H16 O2'
_chemical_formula_weight         204.26
_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             2018-12-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-28 deposited with the CCDC.    2019-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.2989(3)
_cell_length_b                   10.0377(5)
_cell_length_c                   17.5539(9)
_cell_measurement_reflns_used    9821
_cell_measurement_temperature    100
_cell_measurement_theta_max      68.63
_cell_measurement_theta_min      4.40
_cell_volume                     1109.87(10)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_detector                 'Bruker PHOTO 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker PHOTO 100 area detector'
_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  0.0406
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16724
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.606
_diffrn_reflns_theta_min         5.039
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.644
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6372
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0823 before and 0.0515 after correction. The Ratio of minimum to maximum transmission is 0.8461. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.187
_refine_diff_density_min         -0.122
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details
;
 Flack x determined using 825 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.09(8)
_refine_ls_extinction_coef       0.025(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         2026
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0269
_refine_ls_R_factor_gt           0.0268
_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^)+(0.0318P)^2^+0.2051P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0675
_refine_ls_wR_factor_ref         0.0676
_reflns_Friedel_coverage         0.695
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                2016
_reflns_number_total             2026
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01769k2.cif
_cod_data_source_block           cxy0591
_cod_database_code               1551082
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.774
_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.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C8(H8A,H8B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C3(H3), C10(H10), C11(H11)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
2.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_olex2_submission_special_instructions 'No special instructions were received'