Enantioselective Desymmetrization of Bisphenol Derivatives via Ir-Catalyzed Allylic Dearomatization.
Wang, Ye; Zhang, Wen-Yun; Xie, Jia-Hao; Yu, Zong-Lun; Tan, Jia-Hao; Zheng, Chao; Hou, Xue-Long; You, Shu-Li; Journal of the American Chemical Society 142 (2020) 19354–19359; doi:10.1021/jacs.0c09638

data_4135333
_publ_section_title
;
 Enantioselective Desymmetrization of Bisphenol Derivatives via
 Ir-Catalyzed Allylic Dearomatization.
;
_journal_issue                   45
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              19354
_journal_page_last               19359
_journal_paper_doi               10.1021/jacs.0c09638
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C29 H36 O10, H2 O'
_chemical_formula_sum            'C29 H38 O11'
_chemical_formula_weight         562.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-06-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.3636(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.8647(9)
_cell_length_b                   8.5749(3)
_cell_length_c                   12.5880(4)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      70.127
_cell_measurement_theta_min      3.181
_cell_volume                     2999.02(17)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX2'
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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  0.0576
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            27741
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        65.488
_diffrn_reflns_theta_max         65.488
_diffrn_reflns_theta_min         4.564
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.797
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5041
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1624 before and 0.0886 after correction. The Ratio of minimum to maximum transmission is 0.6692. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.246
_exptl_crystal_description       prismatic
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_platon_squeeze_details
;

;
_refine_diff_density_max         0.198
_refine_diff_density_min         -0.132
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 2003 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.26(8)
_refine_ls_extinction_coef       0.0015(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   1.119
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         5021
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0442
_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^)+(0.0410P)^2^+1.8457P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1065
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                4830
_reflns_number_total             5021
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09638_si_003.cif
_cod_data_source_block           cu_d8v17292_0m
_cod_depositor_comments
'Adding full bibliography for 4135332--4135333.cif.'
_cod_database_code               4135333
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.857
_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
 O11-H11A = O11-H11B
 0.82 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C7(H7), C11(H11)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C25(H25A,H25B), C28(H28A,H28B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5A), C12(H12), C18(H18), C21(H21)
3.d X=CH2 refined with riding coordinates:
 C13(H13A,H13B)
3.e Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C26(H26A,H26B,H26C), C29(H29A,H29B,H29C)
3.f Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_shelx_res_checksum              40419
_shelx_hkl_checksum              40198
_olex2_submission_special_instructions 'No special instructions were received'