Nickel-Catalyzed Intermolecular Carbobromination of Alkynes
Takahashi, Toshifumi; Kurahashi, Takuya; Matsubara, Seijiro; ACS Catalysis 10 (2020) 3773–3777; doi:10.1021/acscatal.0c00980

data_4517477
_publ_section_title
;
 Nickel-Catalyzed Intermolecular Carbobromination of Alkynes
;
_journal_issue                   6
_journal_name_full               'ACS Catalysis'
_journal_page_first              3773
_journal_page_last               3777
_journal_paper_doi               10.1021/acscatal.0c00980
_journal_volume                  10
_journal_year                    2020
_chemical_formula_moiety         'C20 H21 Br O'
_chemical_formula_sum            'C20 H21 Br O'
_chemical_formula_weight         357.28
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                80.749(3)
_cell_angle_beta                 86.494(2)
_cell_angle_gamma                89.645(3)
_cell_formula_units_Z            4
_cell_length_a                   9.0497(3)
_cell_length_b                   11.0964(5)
_cell_length_c                   17.4034(5)
_cell_measurement_reflns_used    8966
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.2250
_cell_measurement_theta_min      2.5880
_cell_volume                     1721.66(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.27a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.27a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.27a (Rigaku OD, 2019)'
_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      99.99(10)
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.991
_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    -56.00 -10.00   0.50    3.00    --  -39.45 115.00 109.00   92
  2  \w    -41.00 -16.00   0.50   10.00    --  -94.50  45.00  60.00   50
  3  \w    -71.00 -46.00   0.50   10.00    --  -94.50 115.00 109.00   50
  4  \w     -9.00  41.00   0.50    3.00    --  -39.45  19.00  60.00  100
  5  \w    -12.00  45.00   0.50    3.00    --  -39.45  19.00   0.00  114
  6  \w    -11.00  45.00   0.50    3.00    --  -39.45  19.00 -60.00  112
  7  \w    -33.00  39.00   0.50    3.00    --  -39.45  38.00-120.00  144
  8  \w     74.00 116.00   0.50    3.00    --   39.45 168.00-106.00   84
  9  \w     75.00 120.00   0.50   10.00    --  112.44 168.00-106.00   90
 10  \w     68.00 103.00   0.50   10.00    --  112.44 178.00 -30.00   70
 11  \w    108.00 151.00   0.50   10.00    --  112.44 111.00  60.00   86
 12  \w    141.00 166.00   0.50   10.00    --  112.44 115.00 109.00   50
 13  \w    110.00 177.00   0.50   10.00    --  112.44  77.00  90.00  134
 14  \w    108.00 142.00   0.50   10.00    --  112.44 111.00 120.00   68
 15  \w    105.00 160.00   0.50   10.00    --  112.44  77.00 150.00  110
 16  \w     74.00 120.00   0.50    3.00    --   39.45  38.00 120.00   92
 17  \w     47.00  72.00   0.50   10.00    --  112.44 -61.00  30.00   50
 18  \w     42.00  74.00   0.50   10.00    --  112.44 -61.00   0.00   64
 19  \w     51.00 101.00   0.50   10.00    --  112.44 -94.00 -60.00  100
 20  \w     72.00 102.00   0.50   10.00    --  112.44 -94.00-120.00   60
 21  \w     93.00 118.00   0.50   10.00    --  112.44-168.00-124.00   50
 22  \w     52.00 102.00   0.50   10.00    --  112.44 -94.00 -90.00  100
 23  \w     75.00 100.00   0.50   10.00    --  112.44-115.00  19.00   50
 24  \w     76.00 102.00   0.50   10.00    --  112.44 -94.00  30.00   52
 25  \w     44.00 103.00   0.50   10.00    --  112.44-111.00  30.00  118
 26  \w     76.00 101.00   0.50   10.00    --  112.44-111.00 150.00   50
 27  \w     42.00  67.00   0.50   10.00    --  112.44 -94.00  30.00   50
 28  \w     40.00  68.00   0.50   10.00    --  112.44 -61.00  90.00   56
 29  \w     35.00 102.00   0.50   10.00    --  112.44 -94.00 150.00  134
 30  \w     32.00  93.00   0.50    3.00    --   39.45-115.00  19.00  122
 31  \w     97.00 123.00   0.50    3.00    --   39.45-168.00-124.00   52
 32  \w     57.00  88.00   0.50   10.00    --  112.44 -94.00-180.00   62
 33  \w     32.00 101.00   0.50   10.00    --  112.44 -94.00-150.00  138
 34  \w     86.00 113.00   0.50   10.00    --  112.44  45.00-120.00   54
 35  \w    122.00 178.00   0.50   10.00    --  112.44  45.00-120.00  112
 36  \w    120.00 175.00   0.50   10.00    --  112.44  61.00-180.00  110
 37  \w     85.00 170.00   0.50   10.00    --  112.44  61.00 -30.00  170
 38  \w     84.00 176.00   0.50   10.00    --  112.44  45.00 -90.00  184
 39  \w     69.00 135.00   0.50   10.00    --  112.44 178.00-180.00  132
 40  \w     23.00  71.00   0.50    3.00    --   39.45  38.00 120.00   96
 41  \w    -23.00   3.00   0.50    3.00    --   39.45 -19.00  60.00   52
 42  \w   -118.00 -79.00   0.50    3.00    --  -39.45-168.00-124.00   78
 43  \w    -83.00 -54.00   0.50   10.00    --  -94.50-168.00-124.00   58
 44  \w   -120.00 -88.00   0.50   10.00    --  -94.50-115.00  19.00   64
 45  \w   -141.00-111.00   0.50   10.00    --  -94.50 -45.00  60.00   60
 46  \w   -103.00 -76.00   0.50   10.00    --  -94.50 -45.00  60.00   54
 47  \w    -49.00 -21.00   0.50   10.00    --  -94.50  45.00 -30.00   56
 48  \w    -48.00 -22.00   0.50   10.00    --  -94.50  45.00 -60.00   52
 49  \w    -48.00 -20.00   0.50   10.00    --  -94.50  45.00-120.00   56
 50  \w    -98.00 -73.00   0.50    3.00    --  -39.45 168.00-106.00   50
 51  \w    -73.00 -48.00   0.50   10.00    --  -94.50 168.00-106.00   50
 52  \w   -173.00-147.00   0.50   10.00    --  -94.50 -45.00  60.00   52
 53  \w     70.00  95.00   0.50   10.00    --  112.44 178.00 150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-S'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0111518000
_diffrn_orient_matrix_UB_12      0.1349418000
_diffrn_orient_matrix_UB_13      -0.0385731000
_diffrn_orient_matrix_UB_21      -0.0250026000
_diffrn_orient_matrix_UB_22      -0.0371906000
_diffrn_orient_matrix_UB_23      -0.0797848000
_diffrn_orient_matrix_UB_31      -0.1683423000
_diffrn_orient_matrix_UB_32      0.0139372000
_diffrn_orient_matrix_UB_33      0.0148437000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16856
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.250
_diffrn_reflns_theta_min         2.577
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              PhotonJet-S
_exptl_absorpt_coefficient_mu    3.233
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48652
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.27a (Rigaku Oxford Diffraction, 2019)
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    1.378
_exptl_crystal_description       needle
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.386
_exptl_crystal_size_mid          0.025
_exptl_crystal_size_min          0.024
_refine_diff_density_max         3.428
_refine_diff_density_min         -1.021
_refine_diff_density_rms         0.150
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     401
_refine_ls_number_reflns         6235
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0932
_refine_ls_R_factor_gt           0.0868
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1228P)^2^+9.7447P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2355
_refine_ls_wR_factor_ref         0.2403
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5492
_reflns_number_total             6235
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00980_si_003.cif
_cod_data_source_block           product_2
_cod_depositor_comments
;Adding full bibliography for 4517476--4517477.cif.

 Adding full bibliography for 4517476--4517477.cif.
;
_cod_database_code               4517477
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H21 O Br'
_diffrn_oxdiff_digest_frames
;
014a15fbb235bf629a2954f11b72016ed6043440ab3
;
_diffrn_oxdiff_digest_hkl
;
01726764655515f818c1e659b41417554822b8
;
_reflns_odcompleteness_completeness 99.13
_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 Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C19(H19A,H19B), C37(H37A,H37B), C18(H18A,H18B), C39(H39A,
 H39B), C38(H38A,H38B)
2.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C11(H11), C14(H14), C10(H10), C30(H30), C34(H34), C6(H6), C4(H4),
 C31(H31), C5(H5), C33(H33), C28(H28), C25(H25), C8(H8), C27(H27), C26(H26),
 C24(H24), C7(H7)
2.c Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C40(H40A,H40B,
 H40C)
;
_shelx_res_checksum              97442
_shelx_hkl_checksum              94410
_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 1.856
_oxdiff_exptl_absorpt_empirical_full_min 0.529