Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and Mechanistic Study
Bismuto, Alessandro; Delcaillau, Tristan; Müller, Patrick; Morandi, Bill; ACS Catalysis  (2020) 4630–4639; doi:10.1021/acscatal.0c00393

data_4517532
_publ_section_title
;
 Nickel-Catalyzed Amination of Aryl Thioethers: A Combined Synthetic and
 Mechanistic Study
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4630
_journal_page_last               4639
_journal_paper_doi               10.1021/acscatal.0c00393
_journal_year                    2020
_chemical_formula_moiety         'C13 H13 N O2 S'
_chemical_formula_sum            'C13 H13 N O2 S'
_chemical_formula_weight         247.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.454(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4888(2)
_cell_length_b                   5.60040(10)
_cell_length_c                   15.2060(2)
_cell_measurement_reflns_used    7961
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.1610
_cell_measurement_theta_min      3.6400
_cell_volume                     1163.42(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.42a (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      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_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     37.00 124.00   0.50    5.39    --   48.87  38.00  90.00  174
  2  \w     86.00 176.00   0.50   21.55    --  110.00  77.00  60.00  180
  3  \w    133.00 176.00   0.50   21.55    --  110.00  77.00  90.00   86
  4  \w    136.00 176.00   0.50   21.55    --  110.00  77.00 -30.00   80
  5  \w     94.00 178.00   0.50   21.55    --  110.00  57.00 120.00  168
  6  \w     95.00 120.00   0.50   21.55    --  110.00  57.00  30.00   50
  7  \w     94.00 178.00   0.50   21.55    --  110.00  57.00  90.00  168
  8  \w    105.00 132.00   0.50   21.55    --  110.00  38.00  90.00   54
  9  \w     88.00 122.00   0.50   21.55    --  110.00  77.00 120.00   68
 10  \w     96.00 134.00   0.50   21.55    --  110.00  57.00  60.00   76
 11  \w     86.00 176.00   0.50   21.55    --  110.00  77.00  30.00  180
 12  \w     98.00 176.00   0.50   21.55    --  110.00  19.00 -90.00  156
 13  \w     97.00 175.00   0.50   21.55    --  110.00  19.00-180.00  156
 14  \w     87.00 161.00   0.50   21.55    --  110.00  77.00   0.00  148
 15  \w     87.00 113.00   0.50   21.55    --  110.00  77.00  90.00   52
 16  \w     38.00  68.00   0.50   21.55    --  110.00 -57.00   0.00   60
 17  \w     38.00  68.00   0.50   21.55    --  110.00 -57.00  30.00   60
 18  \w     46.00  90.00   0.50   21.55    --  110.00 -99.00   0.00   88
 19  \w     39.00 118.00   0.50   21.55    --  110.00-125.00 -90.00  158
 20  \w     39.00 117.00   0.50   21.55    --  110.00-125.00  60.00  156
 21  \w    106.00 131.00   0.50   21.55    --  110.00 -77.00  90.00   50
 22  \w     45.00  76.00   0.50   21.55    --  110.00 -77.00  90.00   62
 23  \w    -27.00   9.00   0.50    5.39    --   48.87 -19.00  60.00   72
 24  \w     -9.00  26.00   0.50    5.39    --  -49.62  19.00 -30.00   70
 25  \w     -9.00  26.00   0.50    5.39    --  -49.62  19.00  60.00   70
 26  \w     -9.00  26.00   0.50    5.39    --  -49.62  19.00 120.00   70
 27  \w     -9.00  26.00   0.50    5.39    --  -49.62  19.00 150.00   70
 28  \w    -38.00   6.00   0.50   21.55    --  -70.00  38.00  30.00   88
 29  \w   -116.00 -26.00   0.50    5.39    --  -49.62 -77.00  60.00  180
 30  \w   -125.00 -37.00   0.50    5.39    --  -49.62 -38.00 120.00  176
 31  \w   -136.00 -46.00   0.50   21.55    --  -70.00 -77.00 150.00  180
 32  \w   -137.00 -44.00   0.50   21.55    --  -70.00 -82.00  62.94  186
 33  \w   -136.00 -46.00   0.50   21.55    --  -70.00 -77.00  44.30  180
 34  \w   -140.00 -82.00   0.50   21.55    --  -70.00 -99.00 -90.00  116
 35  \w   -136.00 -46.00   0.50   21.55    --  -70.00 -77.00  90.00  180
 36  \w   -141.00 -68.00   0.50   21.55    --  -70.00-128.00 130.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0131630000
_diffrn_orient_matrix_UB_12      -0.0170026000
_diffrn_orient_matrix_UB_13      0.1045889000
_diffrn_orient_matrix_UB_21      -0.0987035000
_diffrn_orient_matrix_UB_22      -0.1317610000
_diffrn_orient_matrix_UB_23      -0.0239816000
_diffrn_orient_matrix_UB_31      0.0530306000
_diffrn_orient_matrix_UB_32      -0.2407822000
_diffrn_orient_matrix_UB_33      0.0056886000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0504
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            17444
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.554
_diffrn_reflns_theta_min         3.651
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.382
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.721
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.42a (Rigaku Oxford Diffraction, 2019)
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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_description       needle
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.166
_exptl_crystal_size_mid          0.023
_exptl_crystal_size_min          0.016
_refine_diff_density_max         0.603
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     158
_refine_ls_number_reflns         2478
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0725P)^2^+0.4823P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1154
_refine_ls_wR_factor_ref         0.1203
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2158
_reflns_number_total             2478
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00393_si_003.cif
_cod_data_source_block           bm130919_1_1
_cod_depositor_comments
'Adding full bibliography for 4517528--4517534.cif.'
_cod_database_code               4517532
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C13H13NO2S
_diffrn_oxdiff_digest_frames
;
0107c7f256d20dc5025fd028b0545d01b30421419bd
;
_diffrn_oxdiff_digest_hkl
;
01c1377be0128eedddc035277e1f05693150cd
;
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.93 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13)
3.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              99101
_shelx_hkl_checksum              30269
_olex2_date_sample_data_collection 2019-09-13
_olex2_date_sample_submission    2019-09-13
_olex2_submission_original_sample_id bm130919_1_1
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.297
_oxdiff_exptl_absorpt_empirical_full_min 0.605