Enantioselective Hydroboration of Ketones Catalyzed by Rare-Earth Metal Complexes Containing Trost Ligands.
Sun, Yuli; Lu, Chengrong; Zhao, Bei; Xue, Mingqiang; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00877

data_4038647
_publ_section_title
;
 Enantioselective Hydroboration of Ketones Catalyzed by Rare-Earth Metal
 Complexes Containing Trost Ligands.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00877
_journal_year                    2020
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C86 H86 Eu2 N4 O6, C4 H10 O2, C4 H8 O'
_chemical_formula_sum            'C94 H104 Eu2 N4 O9'
_chemical_formula_weight         1737.73
_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             2020-02-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.5692(7)
_cell_length_b                   16.6420(8)
_cell_length_c                   37.3230(17)
_cell_measurement_reflns_used    9442
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.50
_cell_measurement_theta_min      2.48
_cell_volume                     9049.4(7)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            230487
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.541
_diffrn_reflns_theta_min         2.153
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.428
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       block
_exptl_crystal_F_000             3576
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.438
_refine_diff_density_min         -1.228
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 8567 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     956
_refine_ls_number_reflns         20816
_refine_ls_number_restraints     2221
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0287
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0302P)^2^+13.5673P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0683
_refine_ls_wR_factor_ref         0.0699
_reflns_Friedel_coverage         0.839
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                19672
_reflns_number_total             20816
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00877_si_002.cif
_cod_data_source_block           b180506c_0ma_a_sq
_cod_database_code               4038647
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.599
_shelx_estimated_absorpt_t_min   0.535
_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
2. Rigid bond restraints
 C13, C20
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
3. Uiso/Uaniso restraints and constraints
C69 \\sim C5 \\sim C30 \\sim C47 \\sim C4 \\sim C48 \\sim C81 \\sim C27 \\sim
C40 \\sim C32 \\sim C49 \\sim C3 \\sim C31 \\sim C75 \\sim C70 \\sim C51 \\sim
C39 \\sim C8 \\sim C46 \\sim C38 \\sim C41 \\sim C6 \\sim C73 \\sim C12 \\sim
C74 \\sim C26 \\sim C2 \\sim C82 \\sim C80 \\sim C57 \\sim C50 \\sim C53 \\sim
C9 \\sim C15 \\sim C7 \\sim C45 \\sim C63 \\sim C29 \\sim C37 \\sim C36 \\sim
C54 \\sim C42 \\sim C13 \\sim C86 \\sim C56 \\sim C55 \\sim C72 \\sim C11 \\sim
C14 \\sim C43 \\sim C76 \\sim C33 \\sim C58 \\sim C71 \\sim C52 \\sim C78 \\sim
C68 \\sim C59 \\sim C44 \\sim C64 \\sim C83 \\sim C79 \\sim C84 \\sim C77 \\sim
C21 \\sim C28 \\sim C35 \\sim C1 \\sim C10 \\sim C85 \\sim C20 \\sim C16 \\sim
C22 \\sim C19 \\sim C91 \\sim C34 \\sim C62 \\sim C61 \\sim C65 \\sim C89 \\sim
C60 \\sim C67 \\sim C17 \\sim C93 \\sim C66 \\sim C25 \\sim C92 \\sim C94 \\sim
C88 \\sim C18 \\sim C90 \\sim C23 \\sim C87 \\sim C24: within 3.8A with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C66) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25) = Uanis(C24)
Uanis(C24) = Uanis(C23) = Uanis(C22) = Uanis(C21) = Uanis(C20) = Uanis(C25)
4.a Ternary CH refined with riding coordinates:
 C30(H30), C73(H73), C12(H12), C55(H55)
4.b Secondary CH2 refined with riding coordinates:
 C69(H69A,H69B), C27(H27A,H27B), C70(H70A,H70B), C51(H51A,H51B), C8(H8A,H8B),
 C26(H26A,H26B), C53(H53A,H53B), C9(H9A,H9B), C29(H29A,H29B), C54(H54A,H54B),
 C72(H72A,H72B), C11(H11A,H11B), C71(H71A,H71B), C52(H52A,H52B), C28(H28A,H28B),
  C10(H10A,H10B), C89(H89A,H89B), C93(H93A,H93B), C92(H92A,H92B), C88(H88A,
 H88B), C90(H90A,H90B), C87(H87A,H87B)
4.c Aromatic/amide H refined with riding coordinates:
 C40(H40), C3(H3), C39(H39), C46(H46), C41(H41), C82(H82), C80(H80), C50(H50),
 C15(H15), C7(H7), C37(H37), C36(H36), C42(H42), C86(H86), C43(H43), C76(H76),
 C33(H33), C58(H58), C78(H78), C68(H68), C59(H59), C64(H64), C83(H83), C79(H79),
  C84(H84), C77(H77), C21(H21), C35(H35), C85(H85), C16(H16), C22(H22),
 C19(H19), C34(H34), C62(H62), C61(H61), C65(H65), C60(H60), C67(H67), C17(H17),
  C66(H66), C25(H25), C18(H18), C23(H23), C24(H24)
4.d Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C1(H1A,H1B,H1C), C91(H91A,H91B,H91C), C94(H94A,H94B,H94C)
;
_shelx_res_checksum              13306
_shelx_hkl_checksum              11274
_shelx_fab_checksum              79879
_olex2_submission_special_instructions 'No special instructions were received'