Nickel-catalyzed diastereoselective hydroboration of acrylates with a vinylborane reagent.
Hu, Guanwen; Zhang, Peiqi; Wang, Xinmou; Wan, Chunteng; Fu, Yiyi; Leung, Wa Hung; Lin, Zhenyang; Quan, Yangjian; Chemical science 16 (2025) 13449–13458; doi:10.1039/d5sc02695d

data_1574871
_publ_section_title
;
 Nickel-catalyzed diastereoselective hydroboration of acrylates with a
 vinylborane reagent.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              13449
_journal_page_last               13458
_journal_paper_doi               10.1039/d5sc02695d
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C43 H37 B F6 N2 Ni P2, 0.375(C6 H14), 0.125(C6 H12)'
_chemical_formula_sum            'C46 H43.75 B F6 N2 Ni P2'
_chemical_formula_weight         870.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-06-03
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-03 deposited with the CCDC.	2025-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.2828(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.01864(11)
_cell_length_b                   11.91416(9)
_cell_length_c                   28.8690(2)
_cell_measurement_reflns_used    7886
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      73.1340
_cell_measurement_theta_min      4.0180
_cell_volume                     4130.53(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5-alpha (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3577
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -1.50  42.00   0.75   16.00    --   36.13  77.00  30.00   58
  2  \w    -37.00  72.50   0.75   16.00    --   36.13 -37.00   0.00  146
  3  \w      0.00 119.25   0.75   16.00    --   36.13  57.00-150.00  159
  4  \w     25.00 146.50   0.75   48.00    --  109.64 -61.00  90.00  162
  5  \w    103.00 172.00   0.75   48.00    --  109.64  77.00  90.00   92
  6  \w    132.00 172.50   0.75   48.00    --  109.64 111.00 120.00   54
  7  \w    103.00 170.50   0.75   48.00    --  109.64  77.00-150.00   90
  8  \w     74.00 176.00   0.75   48.00    --  109.64  30.00-180.00  136
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0650395000
_diffrn_orient_matrix_UB_12      0.1114478000
_diffrn_orient_matrix_UB_13      0.0020523000
_diffrn_orient_matrix_UB_21      0.0653592000
_diffrn_orient_matrix_UB_22      -0.0365910000
_diffrn_orient_matrix_UB_23      -0.0423144000
_diffrn_orient_matrix_UB_31      -0.0891542000
_diffrn_orient_matrix_UB_32      0.0543318000
_diffrn_orient_matrix_UB_33      -0.0325563000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0136
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            12865
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.991
_diffrn_reflns_theta_min         3.681
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.943
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86697
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.399
_exptl_crystal_description       block
_exptl_crystal_F_000             1803
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.767
_refine_diff_density_min         -0.531
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     600
_refine_ls_number_reflns         7963
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0349
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0497P)^2^+2.8215P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0903
_refine_ls_wR_factor_ref         0.0947
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6998
_reflns_number_total             7963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02695d2.cif
_cod_data_source_block           ghuaf4_cu100k_auto
_cod_depositor_comments
'Adding full bibliography for 1574870--1574872.cif.'
_cod_database_code               1574871
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.759
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H1SA,H1SB,H1SC} of C1S, All C(H,H) groups
 At 1.5 times of:
  {H6A,H6B,H6C} of C6, {H7A,H7B,H7C} of C7
2. Restrained distances
 C11S-C12S = C13S-C12S
 1.52 with sigma of 0.01
 C11S_$1-C13S
 1.52 with sigma of 0.01
 C11S-C13S
 2.45 with sigma of 0.02
 F4A-C44 \\sim F4-C44
 with sigma of 0.02
 F3-C34 \\sim F3A-C34
 with sigma of 0.02
 F2A-C24 \\sim F2-C24
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C12S) \\sim Ueq, Uanis(C13S) \\sim Ueq, Uanis(C11S) \\sim Ueq: with sigma
of 0.003 and sigma for terminal atoms of 0.008
Uanis(F4A) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.008
Uanis(F2A) \\sim Ueq, Uanis(F2) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.008
Uanis(F3A) \\sim Ueq, Uanis(F3) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.008
4. Rigid body (RIGU) restrains
 C11S, C12S, C13S
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: F2(0.5) F2A(0.5) F3(0.5) F3A(0.5) F4(0.5) F4A(0.5) C1S(0.75)
 H1SA(0.75) H1SB(0.75) H1SC(0.75) C2S(0.75) H2SA(0.75) H2SB(0.75) C3S(0.75)
 H3SA(0.75) H3SB(0.75) C11S(0.25) H11A(0.25) H11B(0.25) C12S(0.25) H12A(0.25)
 H12B(0.25) C13S(0.25) H13A(0.25) H13B(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C3S(H3SA,H3SB), C11S(H11A,H11B), C12S(H12A,H12B), C13S(H13A,
 H13B)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C12(H12), C13(H13), C15(H15), C16(H16), C22(H22), C23(H23),
 C25(H25), C26(H26), C32(H32), C33(H33), C35(H35), C36(H36), C42(H42), C43(H43),
  C45(H45), C46(H46), C52(H52), C53(H53), C55(H55), C56(H56), C62(H62),
 C63(H63), C65(H65), C66(H66)
6.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C1S(H1SA,H1SB,H1SC)
;
_shelx_res_checksum              1847
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.229
_oxdiff_exptl_absorpt_empirical_full_min 0.887