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_1550257
_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 rm
_chemical_formula_moiety         'C30 H41 B N2 O2'
_chemical_formula_sum            'C30 H41 B N2 O2'
_chemical_formula_weight         472.46
_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             2018-08-28
_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                 95.8720(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.10720(10)
_cell_length_b                   15.5083(2)
_cell_length_c                   9.60940(10)
_cell_measurement_reflns_used    7754
_cell_measurement_temperature    149.9(2)
_cell_measurement_theta_max      70.7510
_cell_measurement_theta_min      4.5990
_cell_volume                     1350.08(3)
_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      149.9(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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     85.00 144.00   0.50    0.50    --   55.00  53.00 139.00  118
  2  \w     44.00  70.00   0.50    0.50    --   55.00  53.00 139.00   52
  3  \w     71.00 198.00   0.50    1.00    --  110.00  53.00 139.00  254
  4  \w    -55.00 -25.00   0.50    0.50    --    0.00  40.00 -60.00   60
  5  \w    -89.00 -60.00   0.50    0.50    --    0.00  40.00 -60.00   58
  6  \w     52.00  86.00   0.50    0.50    --    0.00  53.00 139.00   68
  7  \w    -20.00  48.00   0.50    0.50    --    0.00  40.00 -60.00  136
  8  \w    -60.00 -13.00   0.50    0.50    --    0.00  53.00 139.00   94
  9  \w     52.00  80.00   0.50    0.50    --   55.00  40.00-120.00   56
 10  \w    112.00 144.00   0.50    0.50    --   55.00  50.00 -60.00   64
 11  \w     37.00  93.00   0.50    0.50    --   55.00  20.00 -90.00  112
 12  \w     15.00 144.00   0.50    0.50    --   55.00  50.00  60.00  258
 13  \w    -17.00 140.00   0.50    0.50    --   55.00  40.00  90.00  314
 14  \w    -32.00  45.00   0.50    0.50    --   55.00  40.00-120.00  154
 15  \w    -21.00   5.00   0.50    0.50    --   55.00  50.00 -60.00   52
 16  \w    -32.00 142.00   0.50    0.50    --   55.00  30.00-150.00  348
 17  \w     21.00  49.00   0.50    1.00    --  110.00  20.00 -90.00   56
 18  \w    125.00 154.00   0.50    1.00    --  110.00  20.00-150.00   58
 19  \w     70.00  96.00   0.50    1.00    --  110.00  40.00-150.00   52
 20  \w     21.00  47.00   0.50    1.00    --  110.00  40.00-150.00   52
 21  \w     21.00  48.00   0.50    1.00    --  110.00  20.00 -60.00   54
 22  \w     21.00  47.00   0.50    1.00    --  110.00  40.00-120.00   52
 23  \w     21.00 105.00   0.50    1.00    --  110.00  20.00  90.00  168
 24  \w     21.00  47.00   0.50    1.00    --  110.00  30.00 -60.00   52
 25  \w     89.00 164.00   0.50    1.00    --  110.00  40.00  60.00  150
 26  \w     22.00  47.00   0.50    1.00    --  110.00  20.00  60.00   50
 27  \w     24.00 102.00   0.50    1.00    --  110.00  10.00  60.00  156
 28  \w    146.00 172.00   0.50    1.00    --  110.00  20.00 -60.00   52
 29  \w     21.00 120.00   0.50    1.00    --  110.00  20.00-150.00  198
 30  \w     21.00  86.00   0.50    1.00    --  110.00  10.00 -60.00  130
 31  \w     21.00  47.00   0.50    1.00    --  110.00  30.00  60.00   52
 32  \w     22.00  47.00   0.50    1.00    --  110.00  40.00  60.00   50
 33  \w     23.00  48.00   0.50    1.00    --  110.00  20.00-120.00   50
 34  \w    123.00 148.00   0.50    1.00    --  110.00  40.00-180.00   50
 35  \w     22.00  48.00   0.50    1.00    --  110.00  30.00 -90.00   52
 36  \w     22.00  52.00   0.50    1.00    --  110.00  40.00-180.00   60
 37  \w    159.00 185.00   0.50    1.00    --  110.00  40.00 -90.00   52
 38  \w     21.00  47.00   0.50    1.00    --  110.00  30.00-120.00   52
 39  \w     69.00  94.00   0.50    1.00    --  110.00  30.00 -90.00   50
 40  \w     35.00  85.00   0.50    1.00    --  110.00   0.00-180.00  100
 41  \w     21.00  92.00   0.50    1.00    --  110.00  10.00-120.00  142
 42  \w     21.00 173.00   0.50    1.00    --  110.00  40.00  30.00  304
 43  \w     22.00 175.00   0.50    1.00    --  110.00  40.00 120.00  306
 44  \w     23.00  49.00   0.50    1.00    --  110.00  40.00  90.00   52
 45  \w     22.00  48.00   0.50    1.00    --  110.00  30.00-150.00   52
 46  \w     21.00  47.00   0.50    1.00    --  110.00  40.00 -90.00   52
 47  \w     21.00  47.00   0.50    1.00    --  110.00  30.00  90.00   52
 48  \w    154.00 186.00   0.50    1.00    --  110.00  30.00  90.00   64
 49  \w    124.00 151.00   0.50    1.00    --  110.00  40.00-120.00   54
;
_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      -0.0374912000
_diffrn_orient_matrix_UB_12      -0.0523359000
_diffrn_orient_matrix_UB_13      0.1279729000
_diffrn_orient_matrix_UB_21      0.1317116000
_diffrn_orient_matrix_UB_22      -0.0602125000
_diffrn_orient_matrix_UB_23      -0.0162917000
_diffrn_orient_matrix_UB_31      0.1008064000
_diffrn_orient_matrix_UB_32      0.0592002000
_diffrn_orient_matrix_UB_33      0.0965816000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            13740
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.945
_diffrn_reflns_theta_min         4.626
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.551
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.19608
_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_density_diffrn    1.162
_exptl_crystal_description       block
_exptl_crystal_F_000             512
_exptl_crystal_recrystallization_method
'Crystallised by slow cooling of a hot hexane solution'
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.129
_refine_diff_density_min         -0.137
_refine_diff_density_rms         0.027
_refine_ls_abs_structure_details
;
 Flack x determined using 2166 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     329
_refine_ls_number_reflns         5068
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0299
_refine_ls_R_factor_gt           0.0284
_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^)+(0.0425P)^2^+0.0927P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0704
_refine_ls_wR_factor_ref         0.0712
_reflns_Friedel_coverage         0.891
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                4852
_reflns_number_total             5068
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04305a3.cif
_cod_data_source_block           lmji9
_cod_database_code               1550257
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C20H20B1N2O2
_chemical_oxdiff_usercomment     JER410
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.973
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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:
 C009(H009), C00C(H00D), C00E(H00E), C00F(H00F)
2.b Secondary CH2 refined with riding coordinates:
 C008(H00A,H00B), C00I(H00I,H00J), C00Q(H00R,H00S), C00R(H00T,H00U)
2.c Aromatic/amide H refined with riding coordinates:
 C00B(H00C), C00G(H00G), C00H(H00H), C00J(H00K), C00K(H00L), C00L(H00M),
 C00M(H00N), C00N(H00O), C00O(H00P), C00P(H00Q), C00U(H00Z), C00V(H00)
2.d Idealised Me refined as rotating group:
 C00S(H00V,H00W,H00X), C00T(H00Y,H,HA), C00W(H0AA,HB,HC), C00X(H1AA,HD,HE),
 C00Y(H2AA,HF,HG)
;
_shelx_res_checksum              46102
_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 4.302
_oxdiff_exptl_absorpt_empirical_full_min 0.626