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_1550259
_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         'C9 H15 B N2 O2'
_chemical_formula_sum            'C9 H15 B N2 O2'
_chemical_formula_weight         194.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-01
_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                 100.885(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6843(3)
_cell_length_b                   10.1231(2)
_cell_length_c                   12.0573(3)
_cell_measurement_reflns_used    3480
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      70.3550
_cell_measurement_theta_min      5.7360
_cell_volume                     1040.91(5)
_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_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.951
_diffrn_measured_fraction_theta_max 0.937
_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     16.00  81.00   0.50    0.50    --    0.00  40.00 120.00  130
  2  \w    -65.00   5.00   0.50    0.50    --    0.00  40.00 120.00  140
  3  \w    105.00 133.00   0.50    0.50    --   55.00  30.00-180.00   56
  4  \w     79.00 106.00   0.50    0.50    --   55.00  50.00  90.00   54
  5  \w    -26.00   1.00   0.50    0.50    --   55.00  20.00  30.00   54
  6  \w    -32.00 140.00   0.50    0.50    --   55.00  50.00-180.00  344
  7  \w      7.00  66.00   0.50    0.50    --   55.00  50.00 150.00  118
  8  \w     61.00 144.00   0.50    0.50    --   55.00  50.00  60.00  166
  9  \w    -34.00   4.00   0.50    0.50    --   55.00  50.00  30.00   76
 10  \w    -34.00  48.00   0.50    0.50    --   55.00  50.00  60.00  164
 11  \w      8.00 135.00   0.50    0.50    --   55.00  50.00  30.00  254
 12  \w    -31.00  77.00   0.50    0.50    --   55.00  50.00  90.00  216
 13  \w     87.00 127.00   0.50    0.50    --   55.00  50.00 150.00   80
 14  \w     73.00 105.00   0.50    0.80    --  110.00  40.00 -90.00   64
 15  \w     63.00  90.00   0.50    0.80    --  110.00  40.00-180.00   54
 16  \w     21.00  60.00   0.50    0.80    --  110.00  40.00-180.00   78
 17  \w    111.00 198.00   0.50    0.80    --  110.00  40.00 120.00  174
 18  \w     26.00  58.00   0.50    0.80    --  110.00  40.00 120.00   64
 19  \w    146.00 173.00   0.50    0.80    --  110.00  40.00-150.00   54
 20  \w    145.00 172.00   0.50    0.80    --  110.00  40.00 150.00   54
 21  \w     23.00  91.00   0.50    0.80    --  110.00  40.00-150.00  136
 22  \w    115.00 199.00   0.50    0.80    --  110.00  40.00 -30.00  168
 23  \w     94.00 197.00   0.50    0.80    --  110.00  40.00  30.00  206
 24  \w     68.00 108.00   0.50    0.80    --  110.00  40.00 120.00   80
 25  \w     87.00 123.00   0.50    0.80    --  110.00  40.00 150.00   72
 26  \w    100.00 127.00   0.50    0.80    --  110.00  40.00  60.00   54
 27  \w     22.00  83.00   0.50    0.80    --  110.00  40.00  30.00  122
 28  \w    115.00 176.00   0.50    0.80    --  110.00  40.00  90.00  122
 29  \w     94.00 125.00   0.50    0.80    --  110.00  40.00-180.00   62
 30  \w    141.00 166.00   0.50    0.80    --  110.00  40.00-180.00   50
 31  \w    123.00 150.00   0.50    0.80    --  110.00  40.00 -60.00   54
 32  \w    168.00 195.00   0.50    0.80    --  110.00  40.00-180.00   54
 33  \w    141.00 195.00   0.50    0.80    --  110.00  40.00 -90.00  108
 34  \w     21.00 165.00   0.50    0.80    --  110.00  40.00-120.00  288
 35  \w     87.00 197.00   0.50    0.80    --  110.00   0.00   0.00  220
 36  \w    132.00 157.00   0.50    0.80    --  110.00  40.00  60.00   50
 37  \w     23.00  83.00   0.50    0.80    --  110.00   0.00   0.00  120
;
_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      0.0370435000
_diffrn_orient_matrix_UB_12      -0.1488520000
_diffrn_orient_matrix_UB_13      0.0107662000
_diffrn_orient_matrix_UB_21      -0.0418519000
_diffrn_orient_matrix_UB_22      -0.0142815000
_diffrn_orient_matrix_UB_23      -0.1294340000
_diffrn_orient_matrix_UB_31      0.1717178000
_diffrn_orient_matrix_UB_32      0.0285231000
_diffrn_orient_matrix_UB_33      -0.0079678000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0243
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_Laue_measured_fraction_full 0.951
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            8522
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.968
_diffrn_reflns_theta_min         5.750
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28519
_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    1.238
_exptl_crystal_description       plate
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.472
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.116
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     153
_refine_ls_number_reflns         1892
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0614
_refine_ls_R_factor_gt           0.0583
_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^)+(0.1002P)^2^+0.2816P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1531
_refine_ls_wR_factor_ref         0.1562
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1768
_reflns_number_total             1892
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04305a3.cif
_cod_data_source_block           lmji8
_cod_database_code               1550259
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C10H12N2B1O2
_chemical_oxdiff_usercomment     JER385
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.946
_reflns_odcompleteness_completeness 94.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H7(0.042) H6(0.043) H2(0.037) H9A(0.064) H9B(0.064) H9C(0.064)
 H8A(0.06) H8B(0.06) H8C(0.06)
 Fixed X: H7(0.337889) H6(0.142941) H2(0.075746) H9A(0.125106) H9B(0.090187)
 H9C(-0.015287) H8A(0.42234) H8B(0.531778) H8C(0.54942)
 Fixed Y: H7(0.653905) H6(0.682176) H2(0.176915) H9A(0.389675) H9B(0.541537)
 H9C(0.449616) H8A(0.352936) H8B(0.475835) H8C(0.352494)
 Fixed Z: H7(0.639654) H6(0.465276) H2(0.434416) H9A(0.286668) H9B(0.275717)
 H9C(0.334744) H8A(0.721678) H8B(0.720242) H8C(0.645017)
;
_shelx_res_checksum              50755
_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 3.047
_oxdiff_exptl_absorpt_empirical_full_min 0.641