Reductive α-borylation of α,β-unsaturated esters using NHC-BH3 activated by I2 as a metal-free route to α-boryl esters.
Radcliffe, James; Fasano, Valerio; Adams, Ralph W.; You, Peiran; Ingleson, Michael James; Chemical Science  (2019) –; doi:10.1039/C8SC04305A

data_1550258
_publ_section_title
;
 Reductive \a-borylation of \a,\b-unsaturated esters using NHC-BH3
 activated by I2 as a metal-free route to \a-boryl esters.
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC04305A
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C10 H17 B F2 N2 O2'
_chemical_formula_sum            'C10 H17 B F2 N2 O2'
_chemical_formula_weight         246.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-08-30 deposited with the CCDC.
2018-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.529(13)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.6658(8)
_cell_length_b                   13.0852(10)
_cell_length_c                   7.7113(8)
_cell_measurement_reflns_used    4058
_cell_measurement_temperature    150
_cell_measurement_theta_max      70.4820
_cell_measurement_theta_min      3.3490
_cell_volume                     621.28(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.21a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.21a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.21a (Rigaku OD, 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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.971
_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    -77.00 -43.00   0.50    0.50    --    0.00  29.00 120.00   68
  2  \w    -37.00  20.00   0.50    0.50    --    0.00  29.00 120.00  114
  3  \w     27.00  65.00   0.50    0.50    --   55.00  14.00  30.00   76
  4  \w    -12.00 143.00   0.50    0.50    --   55.00  43.00 -30.00  310
  5  \w    -34.00 139.00   0.50    0.50    --   55.00  60.00 -60.00  346
  6  \w    -18.00   7.00   0.50    0.50    --   55.00  14.00  30.00   50
  7  \w    -33.00  47.00   0.50    0.50    --   55.00  43.00  60.00  160
  8  \w     53.00 115.00   0.50    0.50    --   55.00  43.00  60.00  124
  9  \w    -18.00  15.00   0.50    0.50    --   55.00  60.00 -90.00   66
 10  \w     12.00  86.00   0.50    0.50    --   55.00  60.00-150.00  148
 11  \w     89.00 119.00   0.50    0.50    --   55.00  14.00  30.00   60
 12  \w     64.00  90.00   0.50    0.50    --  110.00  60.00 -60.00   52
 13  \w    117.00 197.00   0.50    0.50    --  110.00   0.00-120.00  160
 14  \w     47.00 113.00   0.50    0.50    --  110.00  38.00 -60.00  132
 15  \w     79.00 110.00   0.50    0.50    --  110.00   0.00-120.00   62
 16  \w     69.00 198.00   0.50    0.50    --  110.00  29.00  60.00  258
 17  \w     77.00 172.00   0.50    0.50    --  110.00  60.00  90.00  190
 18  \w     90.00 115.00   0.50    0.50    --  110.00  10.00 -60.00   50
 19  \w     24.00  49.00   0.50    0.50    --  110.00  60.00   0.00   50
 20  \w     87.00 181.00   0.50    0.50    --  110.00  60.00  30.00  188
 21  \w     26.00  70.00   0.50    0.50    --  110.00  60.00  90.00   88
 22  \w    143.00 168.00   0.50    0.50    --  110.00  60.00   0.00   50
 23  \w     26.00  83.00   0.50    0.50    --  110.00  60.00-150.00  114
 24  \w    108.00 199.00   0.50    0.50    --  110.00  60.00-150.00  182
 25  \w     31.00  80.00   0.50    0.50    --  110.00  60.00  30.00   98
 26  \w    140.00 198.00   0.50    0.50    --  110.00  60.00-120.00  116
 27  \w     23.00 130.00   0.50    0.50    --  110.00  60.00-120.00  214
 28  \w    128.00 165.00   0.50    0.50    --  110.00  38.00 -60.00   74
 29  \w    146.00 181.00   0.50    0.50    --  110.00  60.00 -60.00   70
 30  \w     23.00  71.00   0.50    0.50    --  110.00  60.00  60.00   96
 31  \w    117.00 184.00   0.50    0.50    --  110.00  10.00 -60.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1594870000
_diffrn_orient_matrix_UB_12      0.0591781000
_diffrn_orient_matrix_UB_13      0.1705265000
_diffrn_orient_matrix_UB_21      -0.0080939000
_diffrn_orient_matrix_UB_22      0.0914464000
_diffrn_orient_matrix_UB_23      -0.1272018000
_diffrn_orient_matrix_UB_31      -0.1925630000
_diffrn_orient_matrix_UB_32      0.0446689000
_diffrn_orient_matrix_UB_33      0.0390241000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            4616
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.919
_diffrn_reflns_theta_min         10.123
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.934
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80635
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.21a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       block
_exptl_crystal_F_000             260
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.415
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1004 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.4(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     158
_refine_ls_number_reflns         2294
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0649
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0950P)^2^+0.5479P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1710
_refine_ls_wR_factor_ref         0.1715
_reflns_Friedel_coverage         0.873
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     0.931
_reflns_number_gt                2263
_reflns_number_total             2294
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04305a3.cif
_cod_data_source_block           lmji4
_cod_database_code               1550258
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C20H20B1N2O2F2
_chemical_oxdiff_usercomment     JER330
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.835
_reflns_odcompleteness_completeness 98.46
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Ternary CH refined with riding coordinates:
 C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C1(H1A,H1B,H1C), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              67765
_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 1.666
_oxdiff_exptl_absorpt_empirical_full_min 0.680