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_1550255
_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_formula_moiety         'C14 H21 B N2 O2'
_chemical_formula_sum            'C14 H21 B N2 O2'
_chemical_formula_weight         260.14
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-15
_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                 111.175(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.1499(9)
_cell_length_b                   7.8915(2)
_cell_length_c                   17.5288(6)
_cell_measurement_reflns_used    5362
_cell_measurement_temperature    149.9(3)
_cell_measurement_theta_max      28.7170
_cell_measurement_theta_min      3.4600
_cell_volume                     2857.09(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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_environment      N~2~
_diffrn_ambient_temperature      149.9(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.893
_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    -17.00  24.00   1.00    4.50    --  -18.77 -99.00 -60.00   41
  2  \w    -11.00  24.00   1.00    4.50    --  -18.77 -99.00-180.00   35
  3  \w    -19.00   7.00   1.00    4.50    --  -18.77  57.00-150.00   26
  4  \w     53.00  89.00   1.00    4.50    --   20.02  57.00  60.00   36
  5  \w      0.00  89.00   1.00    4.50    --   20.02  57.00 -30.00   89
  6  \w     -5.00  93.00   1.00    4.50    --   20.02  37.00-120.00   98
  7  \w     36.00  77.00   1.00    4.50    --   20.02 178.00  90.00   41
  8  \w     18.00  55.00   1.00    4.50    --   20.02  77.00  30.00   37
  9  \w    -49.00  35.00   1.00    4.50    --   20.02 -57.00-180.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0251542000
_diffrn_orient_matrix_UB_12      0.0587549000
_diffrn_orient_matrix_UB_13      -0.0037985000
_diffrn_orient_matrix_UB_21      0.0233710000
_diffrn_orient_matrix_UB_22      0.0623788000
_diffrn_orient_matrix_UB_23      0.0202377000
_diffrn_orient_matrix_UB_31      0.0007961000
_diffrn_orient_matrix_UB_32      0.0271477000
_diffrn_orient_matrix_UB_33      -0.0381872000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.893
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            13067
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.974
_diffrn_reflns_theta_min         2.763
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.080
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.10836
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (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    1.210
_exptl_crystal_description       block
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.9
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.201
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         3381
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0586
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0490P)^2^+1.8190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2814
_reflns_number_total             3381
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04305a3.cif
_cod_data_source_block           amji413
_cod_original_cell_volume        2857.09(18)
_cod_database_code               1550255
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C13H19BN2O2
_chemical_oxdiff_usercomment     JER386
_shelx_estimated_absorpt_t_max   0.976
_shelx_estimated_absorpt_t_min   0.932
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C12(H12), C9(H9), C11(H11), C10(H10)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C5(H5A,H5B,H5C)
;
_shelx_res_checksum              23045
_olex2_date_sample_data_collection 2018-05-15
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 7.547
_oxdiff_exptl_absorpt_empirical_full_min 0.484