Borane-Catalyzed C(sp3)‒F Bond Arylation and Esterification Enabled by Transborylation
Willcox, Dominic R.; Nichol, Gary S.; Thomas, Stephen P.; ACS Catalysis  (2021) 3190–3197; doi:10.1021/acscatal.1c00282

data_4518508
_publ_section_title
;
 Borane-Catalyzed C(sp3)--F Bond Arylation and Esterification Enabled by
 Transborylation
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              3190
_journal_page_last               3197
_journal_paper_doi               10.1021/acscatal.1c00282
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H33 B2 F O2'
_chemical_formula_sum            'C23 H33 B2 F O2'
_chemical_formula_weight         382.11
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-01
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6197)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.252(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3180(2)
_cell_length_b                   29.4659(8)
_cell_length_c                   6.7167(2)
_cell_measurement_reflns_used    6344
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      75.6720
_cell_measurement_theta_min      4.5140
_cell_volume                     2038.78(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.992
_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   -115.00 -69.00   1.00   10.00    --  -41.41-137.00 -32.00   46
  2  \w    -92.00  -9.00   1.00   10.00    --  -41.41 132.00-146.00   83
  3  \w    -95.00 -12.00   1.00   10.00    --  -41.41 137.00  30.00   83
  4  \w     38.00 121.00   1.00   30.00    --  111.00-137.00 -32.00   83
  5  \w     39.00 118.00   1.00   30.00    --  111.00-132.00 144.00   79
  6  \w     91.00 178.00   1.00   30.00    --  111.00 137.00  30.00   87
  7  \w     94.00 178.00   1.00   30.00    --  111.00 132.00-146.00   84
  8  \w   -115.00 -13.00   1.00   10.00    --  -41.41 -57.00 -60.00  102
  9  \w   -116.00 -17.00   1.00   10.00    --  -41.41 -38.00-180.00   99
 10  \w     17.00 116.00   1.00   10.00    --   41.41  38.00 150.00   99
 11  \w    -33.00  66.00   1.00   10.00    --   41.41 -38.00 120.00   99
 12  \w     34.00 104.00   1.00   10.00    --   41.41-137.00 -32.00   70
 13  \w     83.00 178.00   1.00   30.00    --  111.00  30.00  90.00   95
 14  \w     39.00 140.00   1.00   30.00    --  111.00 -61.00  90.00  101
 15  \w     39.00 140.00   1.00   30.00    --  111.00 -61.00 -90.00  101
 16  \w     38.00 112.00   1.00   30.00    --  111.00-125.00  90.00   74
 17  \w     39.00 126.00   1.00   30.00    --  111.00-142.00 -69.60   87
 18  \w    103.00 178.00   1.00   30.00    --  111.00  77.00 -30.00   75
 19  \w    103.00 178.00   1.00   30.00    --  111.00  77.00-150.00   75
 20  \w    103.00 178.00   1.00   30.00    --  111.00  77.00 -90.00   75
 21  \w     28.00 107.00   1.00   30.00    --  111.00 -94.00 -30.00   79
 22  \w     28.00 107.00   1.00   30.00    --  111.00 -94.00   0.00   79
 23  \w     30.00 107.00   1.00   30.00    --  111.00 -99.00 -51.46   77
 24  \w     28.00 107.00   1.00   30.00    --  111.00 -94.00 150.00   79
 25  \w     85.00 178.00   1.00   30.00    --  111.00  45.00 150.00   93
 26  \w     39.00 140.00   1.00   30.00    --  111.00 -61.00 150.00  101
 27  \w     30.00 107.00   1.00   30.00    --  111.00 -99.00 136.63   77
 28  \w     28.00 107.00   1.00   30.00    --  111.00 -94.00-180.00   79
 29  \w     28.00 107.00   1.00   30.00    --  111.00 -94.00  30.00   79
 30  \w     38.00 112.00   1.00   30.00    --  111.00-125.00  60.00   74
 31  \w    103.00 160.00   1.00   30.00    --  111.00  77.00   0.00   57
 32  \w    121.00 147.00   1.00   30.00    --  111.00  77.00 120.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0025561000
_diffrn_orient_matrix_UB_12      0.0522673000
_diffrn_orient_matrix_UB_13      0.0034671000
_diffrn_orient_matrix_UB_21      0.1495259000
_diffrn_orient_matrix_UB_22      -0.0009384000
_diffrn_orient_matrix_UB_23      0.0158943000
_diffrn_orient_matrix_UB_31      0.0018911000
_diffrn_orient_matrix_UB_32      0.0006965000
_diffrn_orient_matrix_UB_33      -0.2291763000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0621
_diffrn_reflns_av_unetI/netI     0.0684
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            16272
_diffrn_reflns_point_group_measured_fraction_full 0.805
_diffrn_reflns_point_group_measured_fraction_max 0.785
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.946
_diffrn_reflns_theta_min         4.547
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.643
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74178
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.245
_exptl_crystal_description       needle
_exptl_crystal_F_000             824
_exptl_crystal_recrystallization_method
'The material was recrystallised from toluene by slow cooling'
_exptl_crystal_size_max          0.388
_exptl_crystal_size_mid          0.033
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.1(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         3336
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0560
_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^)+(0.1146P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1460
_refine_ls_wR_factor_ref         0.1483
_reflns_Friedel_coverage         0.576
_reflns_Friedel_fraction_full    0.611
_reflns_Friedel_fraction_max     0.576
_reflns_number_gt                3121
_reflns_number_total             3336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c00282_si_004.cif
_cod_data_source_block           se20016b
_cod_database_code               4518508
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C92 H128 B8 F4 O8 '
_chemical_oxdiff_usercomment     '@ 120 K DRW03-102'
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.788
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C11-C10 \\sim C11-C10A
 with sigma of 0.02
 C9-C10 \\sim C9-C10A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C9, C10A, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H9BC)=Sof(H9BD)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(H11C)=Sof(H11D)=1-FVAR(1)
 Sof(H9AA)=Sof(H9AB)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H11A)=Sof(H11B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C9(H9AA,H9AB), C9(H9BC,H9BD), C10(H10A,H10B), C10A(H10C,H10D), C11(H11A,H11B),
  C11(H11C,H11D)
;
_shelx_res_checksum              69999
_shelx_hkl_checksum              28663
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id DRW03-102
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 2.154
_oxdiff_exptl_absorpt_empirical_full_min 0.676