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_1550260
_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         'C24 H37 B N2 O2'
_chemical_formula_sum            'C24 H37 B N2 O2'
_chemical_formula_weight         396.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9618(3)
_cell_length_b                   13.0959(3)
_cell_length_c                   15.6088(3)
_cell_measurement_reflns_used    18016
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.7530
_cell_measurement_theta_min      4.3890
_cell_volume                     2445.13(10)
_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      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_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      9.00  34.00   1.00    1.00    --    5.00  53.00  69.00   25
  2  \w    -78.00  40.00   1.00    1.00    --  -45.10  53.00  69.00  118
  3  \w   -106.00 -79.00   1.00    1.00    --  -45.10 -53.00 -75.00   27
  4  \w   -151.00-126.00   1.00    2.00    -- -110.00 -53.00 -75.00   25
  5  \w    -50.00 -21.00   1.00    2.00    -- -110.00  53.00  69.00   29
  6  \w   -112.00 -56.00   1.00    2.00    -- -110.00  53.00  69.00   56
  7  \w    -47.00 -22.00   1.00    1.00    --    5.00 -53.00 -75.00   25
  8  \w    -79.00  34.00   1.00    1.00    --  -45.10  67.00-116.01  113
  9  \w    -77.00 -51.00   1.00    1.00    --  -45.10  46.00 -11.51   26
 10  \w    -49.00  35.00   1.00    1.00    --  -45.10  46.00 -11.51   84
 11  \w   -134.00 -34.00   1.00    1.00    --  -45.10 -64.00-132.05  100
 12  \w    -66.00 -40.00   1.00    2.00    -- -110.00 -19.00  60.00   26
 13  \w   -132.00-106.00   1.00    2.00    -- -110.00 -19.00  60.00   26
 14  \w   -103.00 -32.00   1.00    2.00    -- -110.00  38.00 -60.00   71
 15  \w   -133.00 -50.00   1.00    2.00    -- -110.00  57.00 -60.00   83
 16  \w   -110.00 -70.00   1.00    2.00    -- -110.00 -39.00 167.41   40
 17  \w    -99.00 -72.00   1.00    2.00    -- -110.00 -43.00 157.29   27
 18  \w   -151.00-125.00   1.00    2.00    -- -110.00 -38.00-150.00   26
 19  \w   -143.00 -24.00   1.00    2.00    -- -110.00  76.00  60.00  119
 20  \w   -113.00 -72.00   1.00    2.00    -- -110.00 -76.00-180.00   41
 21  \w    -94.00 -69.00   1.00    2.00    -- -110.00 -38.00-180.00   25
 22  \w   -154.00 -22.00   1.00    2.00    -- -110.00   0.00-120.00  132
 23  \w   -198.00-160.00   1.00    2.00    -- -110.00   0.00-120.00   38
 24  \w   -101.00 -73.00   1.00    2.00    -- -110.00 -76.00-120.00   28
 25  \w   -130.00 -80.00   1.00    2.00    -- -110.00 -57.00   0.00   50
 26  \w   -169.00 -71.00   1.00    2.00    -- -110.00 -76.00 150.00   98
 27  \w   -143.00 -75.00   1.00    2.00    -- -110.00 -43.00 143.50   68
 28  \w   -193.00-167.00   1.00    2.00    -- -110.00 -19.00 -30.00   26
 29  \w   -141.00-115.00   1.00    2.00    -- -110.00 -19.00 -30.00   26
 30  \w   -107.00 -29.00   1.00    2.00    -- -110.00 -19.00 -30.00   78
 31  \w   -118.00 -93.00   1.00    2.00    -- -110.00  57.00-180.00   25
 32  \w    -98.00 -71.00   1.00    2.00    -- -110.00 -38.00-150.00   27
 33  \w   -175.00 -71.00   1.00    2.00    -- -110.00 -42.00 164.68  104
 34  \w   -194.00-169.00   1.00    2.00    -- -110.00 -19.00 120.00   25
 35  \w    -88.00 -28.00   1.00    2.00    -- -110.00 -19.00 120.00   60
 36  \w   -188.00 -87.00   1.00    2.00    -- -110.00 -57.00  30.00  101
 37  \w    -95.00 -70.00   1.00    2.00    -- -110.00 -39.00 141.69   25
 38  \w   -172.00-146.00   1.00    2.00    -- -110.00 -76.00-120.00   26
 39  \w   -158.00-131.00   1.00    2.00    -- -110.00 -38.00-180.00   27
 40  \w   -119.00 -94.00   1.00    2.00    -- -110.00 -76.00  30.00   25
 41  \w   -118.00 -93.00   1.00    2.00    -- -110.00  38.00-150.00   25
 42  \w    -99.00 -74.00   1.00    2.00    -- -110.00  38.00 120.00   25
 43  \w   -139.00-112.00   1.00    2.00    -- -110.00  38.00 -60.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0821619000
_diffrn_orient_matrix_UB_12      -0.0374298000
_diffrn_orient_matrix_UB_13      -0.0690544000
_diffrn_orient_matrix_UB_21      0.0045869000
_diffrn_orient_matrix_UB_22      0.1055336000
_diffrn_orient_matrix_UB_23      -0.0434490000
_diffrn_orient_matrix_UB_31      0.0991877000
_diffrn_orient_matrix_UB_32      -0.0358944000
_diffrn_orient_matrix_UB_33      -0.0554708000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            29288
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.752
_diffrn_reflns_theta_min         4.407
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.520
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81830
_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    1.077
_exptl_crystal_description       plate
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.168
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.38(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         14093
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0436
_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^)+(0.0820P)^2^+0.1123P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1232
_refine_ls_wR_factor_ref         0.1275
_reflns_Friedel_coverage         0.760
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                12865
_reflns_number_total             14093
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 1.6272\% 
 around [-0.56 -0.34 -0.76] (reciprocal) or [-0.73 -0.37 -0.58] (direct)
;
_cod_data_source_file            c8sc04305a3.cif
_cod_data_source_block           rmji6_twin1_hklf4
_cod_database_code               1550260
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C24H37BN2O2
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.903
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7509(12)
 0.2491(12)
2. Fixed Uiso
 At 1.2 times of:
  All B(H,H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Ternary CH refined with riding coordinates:
 C2(H2), C10(H10), C11(H11), C14(H14), C17(H17)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C15(H15A,H15B), C12(H12A,H12B), C13(H13A,H13B), B1(H1A,H1B)
3.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C5(H5), C22(H22), C7(H7), C21(H21), C8(H8), C6(H6)
3.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C19(H19A,H19B,H19C), C16(H16A,H16B,
 H16C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              91478
_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 1.384
_oxdiff_exptl_absorpt_empirical_full_min 0.783
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2