Manganese-Catalyzed C(sp2)‒H Borylation of Furan and Thiophene Derivatives
Britton, Luke; Skrodzki, Maciej; Nichol, Gary S.; Dominey, Andrew P.; Pawluć, Piotr; Docherty, Jamie H.; Thomas, Stephen P.; ACS Catalysis  (2021) 6857–6864; doi:10.1021/acscatal.1c01563

data_4518763
_publ_section_title
;
 Manganese-Catalyzed C(sp2)--H Borylation of Furan and Thiophene
 Derivatives
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              6857
_journal_page_last               6864
_journal_paper_doi               10.1021/acscatal.1c01563
_journal_year                    2021
_chemical_formula_moiety         'C22 H42 B Mn N2 P4'
_chemical_formula_sum            'C22 H42 B Mn N2 P4'
_chemical_formula_weight         524.20
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-07
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_cell_angle_alpha                67.787(2)
_cell_angle_beta                 86.307(2)
_cell_angle_gamma                71.524(2)
_cell_formula_units_Z            2
_cell_length_a                   10.4506(3)
_cell_length_b                   11.3275(3)
_cell_length_c                   13.0799(4)
_cell_measurement_reflns_used    13392
_cell_measurement_temperature    250.00(10)
_cell_measurement_theta_max      75.6410
_cell_measurement_theta_min      4.4270
_cell_volume                     1356.88(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      250.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_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   -100.00 -15.00   1.00    5.00    --  -41.79 143.00-141.00   85
  2  \w    -88.00  -7.00   1.00    5.00    --  -41.79 127.00  48.00   81
  3  \w   -112.00 -65.00   1.00    5.00    --  -41.79-143.00 163.00   47
  4  \w     29.00  98.00   1.00    5.00    --   41.79-127.00 -26.00   69
  5  \w     36.00 108.00   1.00    5.00    --   41.79-143.00 163.00   72
  6  \w     41.00 126.00   1.00   10.00    --  111.00-143.00 163.00   85
  7  \w     96.00 178.00   1.00   10.00    --  111.00 127.00  48.00   82
  8  \w     40.00 114.00   1.00   10.00    --  111.00-127.00 -26.00   74
  9  \w     87.00 171.00   1.00   10.00    --  111.00 143.00-141.00   84
 10  \w      3.00  30.00   1.00    5.00    --   38.00  88.00-150.41   27
 11  \w   -114.00 -19.00   1.00    5.00    --  -41.79 -38.00 -90.00   95
 12  \w   -112.00 -15.00   1.00    5.00    --  -41.79 -57.00  30.00   97
 13  \w   -114.00 -19.00   1.00    5.00    --  -41.79 -38.00 150.00   95
 14  \w     10.00  42.00   1.00    5.00    --   41.79  79.00  -1.76   32
 15  \w     10.00  42.00   1.00    5.00    --   42.00  80.00  59.65   32
 16  \w     13.00  42.00   1.00    5.00    --   46.00  82.00-173.31   29
 17  \w     14.00  42.00   1.00    5.00    --   46.00  79.00 130.62   28
 18  \w     14.00  42.00   1.00    5.00    --   46.00  78.00 -64.78   28
 19  \w     19.00 123.00   1.00    5.00    --   50.00  74.00  -7.23  104
 20  \w     27.00 131.00   1.00    5.00    --   58.00  74.00-103.94  104
 21  \w     28.00 130.00   1.00    5.00    --   58.00  73.00  38.36  102
 22  \w     27.00 131.00   1.00    5.00    --   58.00  74.00 128.93  104
 23  \w     31.00 135.00   1.00    5.00    --   62.00  74.00 167.55  104
 24  \w     32.00 134.00   1.00    5.00    --   62.00  71.00  96.62  102
 25  \w     32.00 134.00   1.00    5.00    --   62.00  73.00-151.88  102
 26  \w     36.00 138.00   1.00    5.00    --   66.00  73.00  55.21  102
 27  \w     36.00 138.00   1.00    5.00    --   66.00  73.00   9.88  102
 28  \w     41.00 141.00   1.00    5.00    --   70.00  69.00 -31.33  100
 29  \w     44.00 146.00   1.00    5.00    --   74.00  72.00 132.47  102
 30  \w     45.00 145.00   1.00    5.00    --   74.00  66.00 -57.12  100
 31  \w     47.00 151.00   1.00   10.00    --   78.00  74.00-137.10  104
 32  \w     52.00 154.00   1.00   10.00    --   82.00  70.00 -28.57  102
 33  \w     53.00 153.00   1.00   10.00    --   82.00  68.00  76.20  100
 34  \w     52.00 154.00   1.00   10.00    --   82.00  71.00-100.33  102
 35  \w     52.00 154.00   1.00   10.00    --   82.00  71.00 100.20  102
 36  \w     55.00 152.00   1.00   10.00    --   82.00  59.00  63.88   97
 37  \w     53.00 153.00   1.00   10.00    --   82.00  66.00-170.32  100
 38  \w     57.00 157.00   1.00   10.00    --   86.00  68.00 140.27  100
 39  \w     57.00 157.00   1.00   10.00    --   86.00  69.00  -2.85  100
 40  \w     61.00 161.00   1.00   10.00    --   90.00  68.00 -77.43  100
 41  \w     66.00 164.00   1.00   10.00    --   94.00  61.00 161.67   98
 42  \w     76.00 178.00   1.00   10.00    --  106.00  72.00 119.52  102
 43  \w     39.00 112.00   1.00   10.00    --  111.00-125.00 -60.00   73
 44  \w     30.00 107.00   1.00   10.00    --  111.00 -94.00-120.00   77
 45  \w     83.00 178.00   1.00   10.00    --  111.00  61.00-120.00   95
 46  \w     40.00 135.00   1.00   10.00    --  111.00 -45.00  60.00   95
 47  \w     85.00 178.00   1.00   10.00    --  111.00  54.00-150.48   93
 48  \w     83.00 178.00   1.00   10.00    --  111.00  61.00  60.00   95
 49  \w     83.00 178.00   1.00   10.00    --  111.00  64.00  18.14   95
 50  \w     83.00 178.00   1.00   10.00    --  111.00  61.00   0.00   95
 51  \w     80.00 178.00   1.00   10.00    --  111.00  74.00 -61.83   98
 52  \w     39.00 112.00   1.00   10.00    --  111.00-125.00  90.00   73
 53  \w     83.00 178.00   1.00   10.00    --  111.00  61.00 -90.00   95
 54  \w     81.00 178.00   1.00   10.00    --  111.00  70.00 -25.25   97
 55  \w     83.00 178.00   1.00   10.00    --  111.00  61.00 120.00   95
 56  \w     81.00 178.00   1.00   10.00    --  111.00  72.00-152.69   97
 57  \w     41.00 139.00   1.00   10.00    --  111.00 -61.00 -30.00   98
 58  \w     39.00 112.00   1.00   10.00    --  111.00-125.00-180.00   73
 59  \w     83.00 178.00   1.00   10.00    --  111.00  61.00-180.00   95
 60  \w     83.00 178.00   1.00   10.00    --  111.00  61.00 -60.00   95
 61  \w     83.00 178.00   1.00   10.00    --  111.00  61.00 -30.00   95
 62  \w     83.00 178.00   1.00   10.00    --  111.00  61.00-150.00   95
 63  \w     83.00 164.00   1.00   10.00    --  111.00  61.00  90.00   81
 64  \w     72.00 110.00   1.00   10.00    --  111.00-125.00  30.00   38
 65  \w     70.00 112.00   1.00   10.00    --  111.00-125.00-150.00   42
 66  \w     53.00 107.00   1.00   10.00    --  111.00 -94.00-150.00   54
 67  \w     87.00 132.00   1.00   10.00    --  111.00  45.00  60.00   45
 68  \w     41.00  97.00   1.00   10.00    --  111.00-125.00   0.00   56
 69  \w     83.00 178.00   1.00   10.00    --  111.00  61.00 150.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0204471000
_diffrn_orient_matrix_UB_12      -0.0853865000
_diffrn_orient_matrix_UB_13      0.1250200000
_diffrn_orient_matrix_UB_21      -0.0957419000
_diffrn_orient_matrix_UB_22      0.1205077000
_diffrn_orient_matrix_UB_23      0.0236196000
_diffrn_orient_matrix_UB_31      -0.1211144000
_diffrn_orient_matrix_UB_32      -0.0466168000
_diffrn_orient_matrix_UB_33      -0.0079058000
_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  0.1246
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            40247
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.076
_diffrn_reflns_theta_min         3.657
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.266
_exptl_absorpt_correction_T_max  0.56016
_exptl_absorpt_correction_T_min  0.52164
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       plate
_exptl_crystal_F_000             556
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of d-benzene and hexane  by slow evaporation'
_exptl_crystal_size_max          0.253
_exptl_crystal_size_mid          0.186
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.599
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         9758
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0576
_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^)+(0.1064P)^2^+0.3340P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1495
_refine_ls_wR_factor_ref         0.1549
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8298
_reflns_number_total             9758
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.8958\% 
 around [0.00 -0.00 1.00] (reciprocal) or [0.07 -0.42 0.91] (direct)
;
_cod_data_source_file            cs1c01563_si_002.cif
_cod_data_source_block           se20013
_cod_database_code               4518763
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C22H42BMnN2P4
_chemical_oxdiff_usercomment     '@ 120 K LAB145'
_shelx_estimated_absorpt_t_max   0.761
_shelx_estimated_absorpt_t_min   0.300
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4830(12)
 0.5170(12)
2. 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
3. Restrained distances
 N2-H2 = N1-H1
 0.84 with sigma of 0.02
4.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C17(H17A,H17B), C18(H18A,H18B)
4.b Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10)
4.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C)
;
_shelx_res_checksum              69362
_shelx_hkl_checksum              86939
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id LAB145
_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 3.922
_oxdiff_exptl_absorpt_empirical_full_min 0.512
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2