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_1550256
_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 H19 B N2 O2'
_chemical_formula_sum            'C10 H19 B N2 O2'
_chemical_formula_weight         210.08
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-13
_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                 111.978(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.6119(2)
_cell_length_b                   12.8257(2)
_cell_length_c                   7.7086(2)
_cell_measurement_reflns_used    5966
_cell_measurement_temperature    150
_cell_measurement_theta_max      74.2800
_cell_measurement_theta_min      6.1920
_cell_volume                     606.20(3)
_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_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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     67.90 254.90   1.00   10.00    --   97.68  73.87 -25.79  187
  2  \w     83.90 268.90   1.00   10.00    --  112.68  73.87  64.21  185
  3  \w    -68.18 116.82   1.00   10.00    --  -39.39  73.87  19.21  185
  4  \f    -25.79 334.43   1.00   10.00  58.16  87.95  73.87    --   360
  5  \w    -68.18 116.82   1.00   10.00    --  -39.39  73.87 -25.79  185
  6  \w     83.90 268.90   1.00   10.00    --  112.68  73.87 124.21  185
  7  \w     83.90 268.90   1.00   10.00    --  112.68  73.87-145.79  185
  8  \w     83.90 268.90   1.00   10.00    --  112.68  73.87  34.21  185
  9  \f    -25.79 334.43   1.00   10.00  28.16  57.95  73.87    --   360
 10  \w     83.90 268.90   1.00   10.00    --  112.68  73.87 154.21  185
 11  \f    -25.79 334.43   1.00   10.00  73.16 102.95  73.87    --   360
 12  \w    -68.18 116.82   1.00   10.00    --  -39.39  73.87  64.21  185
 13  \w     83.90 268.90   1.00   10.00    --  112.68  73.87  94.21  185
 14  \f    -57.29 133.83   1.00   10.00 -11.66  18.13  73.87    --   191
 15  \f    -25.79 334.43   1.00   10.00 -72.95 -43.16  73.87    --   360
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Prospector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0168801000
_diffrn_orient_matrix_UB_12      -0.0208445000
_diffrn_orient_matrix_UB_13      -0.2017467000
_diffrn_orient_matrix_UB_21      0.2187942000
_diffrn_orient_matrix_UB_22      -0.0589464000
_diffrn_orient_matrix_UB_23      0.0755778000
_diffrn_orient_matrix_UB_31      -0.1222963000
_diffrn_orient_matrix_UB_32      -0.1025967000
_diffrn_orient_matrix_UB_33      -0.0024195000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0219
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            8208
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.623
_diffrn_reflns_theta_min         6.191
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78286
_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    1.151
_exptl_crystal_description       block
_exptl_crystal_F_000             228
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.160
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1020 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.44(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     148
_refine_ls_number_reflns         2404
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0513P)^2^+0.1182P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0941
_refine_ls_wR_factor_ref         0.0958
_reflns_Friedel_coverage         0.880
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.955
_reflns_number_gt                2279
_reflns_number_total             2404
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04305a3.cif
_cod_data_source_block           xmji86
_cod_database_code               1550256
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 98.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.45
_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(H008)
2.b Secondary CH2 refined with riding coordinates:
 C4(H00M,H00N)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H007), C8(H009)
2.d Idealised Me refined as rotating group:
 C5(H00A,H00B,H00C), C9(H00D,H00E,H00F), C10(H00G,H00H,H00I), C1(H00J,H00K,H00L)
;
_shelx_res_checksum              29907
_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 1.764
_oxdiff_exptl_absorpt_empirical_full_min 0.520