Design and Synthesis of Chiral oxa-Spirocyclic Ligands for Ir-Catalyzed Direct Asymmetric Reduction of Bringmann's Lactones with Molecular H<sub>2</sub>.
Chen, Gen-Qiang; Lin, Bi-Jin; Huang, Jia-Ming; Zhao, Ling-Yu; Chen, Qi-Shu; Jia, Shi-Peng; Yin, Qin; Zhang, Xumu; Journal of the American Chemical Society 140 (2018) 8064–8068; doi:10.1021/jacs.8b03642

data_4132390
_publ_section_title
;
 Design and Synthesis of Chiral oxa-Spirocyclic Ligands for Ir-Catalyzed
 Direct Asymmetric Reduction of Bringmann's Lactones with Molecular
 H<sub>2</sub>.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8064
_journal_page_last               8068
_journal_paper_doi               10.1021/jacs.8b03642
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H12 O4, C4 H8 O2'
_chemical_formula_sum            'C19 H20 O6'
_chemical_formula_weight         344.35
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0820(6)
_cell_length_b                   10.1905(8)
_cell_length_c                   22.8339(18)
_cell_measurement_reflns_used    9770
_cell_measurement_temperature    150
_cell_measurement_theta_max      68.20
_cell_measurement_theta_min      3.87
_cell_volume                     1647.9(2)
_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      150.0
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0399
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            18679
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.204
_diffrn_reflns_theta_min         3.872
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.861
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6864
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0817 before and 0.0568 after correction. The Ratio of minimum to maximum transmission is 0.9114. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.388
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.174
_refine_diff_density_min         -0.132
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1188 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(7)
_refine_ls_extinction_coef       0.0111(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3014
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0264
_refine_ls_R_factor_gt           0.0250
_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^)+(0.0332P)^2^+0.2637P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0627
_refine_ls_wR_factor_ref         0.0636
_reflns_Friedel_coverage         0.713
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2909
_reflns_number_total             3014
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b03642_si_001.cif
_cod_data_source_block           cu_cxy0003_0m
_cod_database_code               4132390
_shelx_shelxl_version_number     2014/7
_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 Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3A), C4(H4A), C12(H12), C13(H13), C14(H14)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C19(H19A,H19B,H19C)
2.d Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
;
_shelx_res_checksum              58986
_shelx_hkl_checksum              1574
_olex2_submission_special_instructions 'No special instructions were received'