Synthesis of chiral boranes <i>via</i> asymmetric insertion of carbenes into B-H bonds catalyzed by the rhodium(I) diene complex.
Ankudinov, Nikita M.; Komarova, Alina A.; Podyacheva, Evgeniya S.; Chusov, Denis A.; Danshina, Anastasia A.; Perekalin, Dmitry S.; Chemical communications (Cambridge, England) 60 (2024) 8601–8604; doi:10.1039/d4cc02969k

data_7133349
_publ_section_title
;
 Synthesis of chiral boranes <i>via</i> asymmetric insertion of carbenes
 into B-H bonds catalyzed by the rhodium(I) diene complex.
;
_journal_issue                   65
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8601
_journal_page_last               8604
_journal_paper_doi               10.1039/d4cc02969k
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C17 H22 B Br N2 O4'
_chemical_formula_sum            'C17 H22 B Br N2 O4'
_chemical_formula_weight         409.08
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-16
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-21 deposited with the CCDC.	2024-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.2775(3)
_cell_length_b                   8.4391(4)
_cell_length_c                   27.6673(14)
_cell_measurement_reflns_used    2696
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      75.7780
_cell_measurement_theta_min      3.1940
_cell_volume                     1932.69(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.117a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.117a 64-bit (release 26-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.117a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.961
_diffrn_measured_fraction_theta_max 0.929
_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   -118.00 -69.00   0.50    7.00    --  -48.14-132.00  89.00   98
  2  \w    -28.00  24.00   0.50    7.00    --  -48.14   7.00 110.00  104
  3  \w    -91.00 -20.00   0.50   28.00    --  -90.00 132.00 158.00  142
  4  \w    -85.00 -21.00   0.50   28.00    --  -90.00 124.00-106.00  128
  5  \w     91.00 178.00   0.50   28.00    --  111.50 132.00 158.00  174
  6  \w     42.00 111.00   0.50   28.00    --  111.50-124.00 174.00  138
  7  \w    116.00 159.00   0.50   28.00    --  111.50   7.00 110.00   86
  8  \w    -26.00  26.00   0.50    7.00    --  -48.14  19.00   0.00  104
  9  \w    -23.00   6.00   0.50    7.00    --   48.14  -7.00 -65.00   58
 10  \w     45.00  70.00   0.50   28.00    --  111.50 -61.00  90.00   50
 11  \w     91.00 178.00   0.50   28.00    --  111.50  77.00-150.00  174
 12  \w     98.00 139.00   0.50   28.00    --  111.50 125.00-120.00   82
 13  \w     45.00  70.00   0.50   28.00    --  111.50 -61.00 -30.00   50
 14  \w     61.00  87.00   0.50   28.00    --  111.50   0.00 -90.00   52
 15  \w     62.00 102.00   0.50   28.00    --  111.50 -95.00-180.00   80
 16  \w    117.00 163.00   0.50   28.00    --  111.50   0.00 -90.00   92
 17  \w    101.00 142.00   0.50   28.00    --  111.50  61.00  90.00   82
 18  \w     66.00  97.00   0.50   28.00    --  111.50-125.00-180.00   62
 19  \w     46.00  77.00   0.50   28.00    --  111.50 -95.00-150.00   62
 20  \w     48.00  83.00   0.50   28.00    --  111.50 -77.00-120.00   70
 21  \w    103.00 129.00   0.50   28.00    --  111.50  45.00  30.00   52
 22  \w     43.00 101.00   0.50   28.00    --  111.50-125.00-150.00  116
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0146374000
_diffrn_orient_matrix_UB_12      -0.1037161000
_diffrn_orient_matrix_UB_13      0.0456038000
_diffrn_orient_matrix_UB_21      0.0066009000
_diffrn_orient_matrix_UB_22      0.1501993000
_diffrn_orient_matrix_UB_23      0.0316213000
_diffrn_orient_matrix_UB_31      -0.1853708000
_diffrn_orient_matrix_UB_32      -0.0027755000
_diffrn_orient_matrix_UB_33      0.0047565000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0754
_diffrn_reflns_av_unetI/netI     0.0602
_diffrn_reflns_Laue_measured_fraction_full 0.961
_diffrn_reflns_Laue_measured_fraction_max 0.929
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            10888
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.565
_diffrn_reflns_theta_min         5.480
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.093
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.717
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.117a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       needle
_exptl_crystal_F_000             840
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.690
_refine_diff_density_min         -0.822
_refine_diff_density_rms         0.135
_refine_ls_abs_structure_details
;
 Flack x determined using 1228 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         3771
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0933
_refine_ls_R_factor_gt           0.0842
_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^)+(0.0210P)^2^+18.4754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2029
_refine_ls_wR_factor_ref         0.2075
_reflns_Friedel_coverage         0.672
_reflns_Friedel_fraction_full    0.938
_reflns_Friedel_fraction_max     0.853
_reflns_number_gt                3276
_reflns_number_total             3771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02969k3.cif
_cod_data_source_block           4e
_cod_depositor_comments          'Adding full bibliography for 7133349.cif.'
_cod_database_code               7133349
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C14 H14 N2 O4 B Br'
_chemical_oxdiff_usercomment     KA22482
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.621
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C9(H9), B1(H1)
1.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
1.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C13(H13), C14(H14), C16(H16), C17(H17)
1.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              60637
_shelx_hkl_checksum              52021
_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 2.114
_oxdiff_exptl_absorpt_empirical_full_min 0.525