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_4038648
_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 N4 Nd2 O6, C4 H10 O2, C4 H8 O'
_chemical_formula_sum            'C94 H104 N4 Nd2 O9'
_chemical_formula_weight         1722.29
_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                   14.6007(10)
_cell_length_b                   16.7977(11)
_cell_length_c                   37.486(3)
_cell_measurement_reflns_used    9572
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      26.25
_cell_measurement_theta_min      2.46
_cell_volume                     9193.7(11)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0902
_diffrn_reflns_av_unetI/netI     0.0572
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            217163
_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         27.566
_diffrn_reflns_theta_min         2.425
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.171
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6209
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1623 before and 0.0718 after correction.
The Ratio of minimum to maximum transmission is 0.8329.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             3552
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.619
_refine_diff_density_min         -0.956
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.023(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     945
_refine_ls_number_reflns         21158
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0598
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0259P)^2^+16.4727P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0814
_refine_ls_wR_factor_ref         0.0862
_reflns_Friedel_coverage         0.842
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                17784
_reflns_number_total             21158
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00877_si_003.cif
_cod_data_source_block           b190926c_0m_a_sq
_cod_database_code               4038648
_shelx_shelxl_version_number     2016/4
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.977(12)
 0.023(12)
2. 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
3. Uiso/Uaniso restraints and constraints
Uanis(C77) = Uanis(C78) = Uanis(C79) = Uanis(C80) = Uanis(C76) = Uanis(C75)
4.a Ternary CH refined with riding coordinates:
 C55(H55), C30(H30), C73(H73), C12(H12)
4.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C8(H8A,H8B), C27(H27A,H27B), C52(H52A,H52B), C51(H51A,H51B),
 C69(H69A,H69B), C10(H10A,H10B), C70(H70A,H70B), C2AA(H2AA,H2AB), C54(H54A,
 H54B), C29(H29A,H29B), C9(H9A,H9B), C28(H28A,H28B), C71(H71A,H71B), C72(H72A,
 H72B), C53(H53A,H53B), C93(HC,HD), C89(HE,HF), C90(HG,HH), C88(HI,HJ), C92(HN,
 HO), C87(HP,HQ)
4.c Aromatic/amide H refined with riding coordinates:
 C50(H50), C65(H65), C3(H3), C46(H46), C7(H7), C64(H64), C66(H66), C37(H37),
 C82(H82), C59(H59), C62(H62), C33(H33), C39(H39), C67(H67), C68(H68), C19(H19),
  C25(H25), C58(H58), C86(H86), C34(H34), C43(H43), C24(H24), C83(H83),
 C60(H60), C15(H15), C35(H35), C76(H76), C77(H77), C78(H78), C79(H79), C80(H80),
  C40(H40), C36(H36), C61(H61), C21(H21), C42(H42), C41(H41), C16(H16),
 C84(H84), C85(H85), C23(H23), C18(H18), C22(H22), C17(H17)
4.d Fitted hexagon refined as free rotating group:
 C75(C76,C77,C78,C79,C80)
4.e Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C91(H,HA,HB), C1(H1A,H1B,H1C), C94(HK,HL,HM)
;
_shelx_res_checksum              60406
_shelx_hkl_checksum              54917
_shelx_fab_checksum              89168
_olex2_submission_special_instructions 'No special instructions were received'