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_4517534
_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         'C14 H19 N'
_chemical_formula_sum            'C14 H19 N'
_chemical_formula_weight         201.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-08-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.6170(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.62050(10)
_cell_length_b                   8.92000(10)
_cell_length_c                   11.97610(10)
_cell_measurement_reflns_used    15267
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.1480
_cell_measurement_theta_min      4.2060
_cell_volume                     1124.543(19)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (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 1.000
_diffrn_measured_fraction_theta_max 0.993
_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     39.00  64.00   0.50    0.33    --   49.37  38.00  30.00   50
  2  \w     67.00 106.00   0.50    0.33    --   49.37  38.00  30.00   78
  3  \w     84.00 109.00   0.50    0.33    --   49.37  62.00 -22.62   50
  4  \w     83.00 110.00   0.50    0.33    --   54.00  80.00 -98.28   54
  5  \w     64.00 128.00   0.50    1.02    --   82.00  65.00 -50.28  128
  6  \w    103.00 145.00   0.50    1.02    --   90.00  83.00  -2.96   84
  7  \w    133.00 173.00   0.50    1.02    --  110.00  77.00  30.00   80
  8  \w    143.00 171.00   0.50    1.02    --  110.00  77.00   0.00   56
  9  \w    132.00 158.00   0.50    1.02    --  110.00  79.00  71.00   52
 10  \w    137.00 178.00   0.50    1.02    --  110.00  57.00 120.00   82
 11  \w    104.00 130.00   0.50    0.33    --   74.00  78.00 163.07   52
 12  \w     94.00 172.00   0.50    1.02    --  110.00  57.00  90.00  156
 13  \w    103.00 171.00   0.50    1.02    --  110.00 125.00 150.00  136
 14  \w     94.00 126.00   0.50    1.02    --  110.00  57.00 150.00   64
 15  \w     96.00 122.00   0.50    1.02    --  110.00  57.00 120.00   52
 16  \w     86.00 137.00   0.50    1.02    --  110.00  77.00 150.00  102
 17  \w     86.00 115.00   0.50    1.02    --  110.00  79.00  71.00   58
 18  \w     87.00 114.00   0.50    1.02    --  110.00  77.00  30.00   54
 19  \w     86.00 167.00   0.50    1.02    --  110.00  77.00 -30.00  162
 20  \w     98.00 124.00   0.50    1.02    --  110.00  57.00-150.00   52
 21  \w     95.00 141.00   0.50    1.02    --  110.00  57.00-120.00   92
 22  \w     99.00 173.00   0.50    1.02    --  110.00  38.00-150.00  148
 23  \w     95.00 130.00   0.50    1.02    --  110.00  57.00 -60.00   70
 24  \w     86.00 171.00   0.50    1.02    --  110.00  77.00 -60.00  170
 25  \w     89.00 162.00   0.50    1.02    --  110.00  77.00-120.00  146
 26  \w     96.00 177.00   0.50    1.02    --  110.00  57.00 -90.00  162
 27  \w     87.00 113.00   0.50    1.02    --  110.00  77.00-180.00   52
 28  \w     52.00  78.00   0.50    0.33    --   74.00  74.00 -77.06   52
 29  \w     50.00  79.00   0.50    0.33    --   74.00  78.00 -45.15   58
 30  \w     50.00  75.00   0.50    0.33    --   74.00  78.00-108.71   50
 31  \w     38.00  92.00   0.50    0.33    --   49.37  38.00-150.00  108
 32  \w     35.00  76.00   0.50    0.33    --   49.37  57.00-120.00   82
 33  \w     39.00 106.00   0.50    0.33    --   49.37  38.00 -60.00  134
 34  \w     65.00  98.00   0.50    1.02    --   90.00  83.00  -2.96   66
 35  \w     70.00 160.00   0.50    1.02    --   94.00  78.00  41.84  180
 36  \w     90.00 132.00   0.50    1.02    --  110.00  77.00   0.00   84
 37  \w     67.00 115.00   0.50    0.33    --   54.00  82.00  32.81   96
 38  \w     59.00  97.00   0.50    0.33    --   49.37  19.00 120.00   76
 39  \w     61.00  94.00   0.50    1.02    --   82.00  71.00 142.33   66
 40  \w     51.00  80.00   0.50    0.33    --   74.00  78.00 163.07   58
 41  \w     37.00  95.00   0.50    0.33    --   49.37  57.00  90.00  116
 42  \w     33.00  71.00   0.50    0.33    --   49.37  62.00 -22.62   76
 43  \w     29.00  54.00   0.50    0.33    --   54.00  82.00  32.81   50
 44  \w     30.00  57.00   0.50    0.33    --   54.00  80.00 -19.10   54
 45  \w     31.00  59.00   0.50    0.33    --   54.00  80.00 -98.28   56
 46  \w     28.00  54.00   0.50    0.33    --   54.00  83.00-157.46   52
 47  \w     38.00  63.00   0.50    0.33    --   62.00  79.00-118.61   50
 48  \w     17.00  42.00   0.50    0.33    --   46.00  89.00  71.45   50
 49  \w     32.00  59.00   0.50    0.33    --   58.00  83.00 134.66   54
 50  \w     38.00  64.00   0.50    1.02    --  110.00 -57.00 -60.00   52
 51  \w     41.00  67.00   0.50    1.02    --  110.00 -57.00 -30.00   52
 52  \w     39.00  66.00   0.50    1.02    --  110.00 -57.00 -90.00   54
 53  \w     40.00 109.00   0.50    1.02    --  110.00 -99.00-120.00  138
 54  \w     66.00 103.00   0.50    1.02    --  110.00 -99.00 -30.00   74
 55  \w     48.00  87.00   0.50    1.02    --  110.00 -99.00 -90.00   78
 56  \w     43.00  87.00   0.50    1.02    --  110.00 -99.00-180.00   88
 57  \w     62.00 121.00   0.50    0.33    --   49.37-178.00 -90.00  118
 58  \w     40.00 118.00   0.50    1.02    --  110.00-125.00 120.00  156
 59  \w     80.00 108.00   0.50    1.02    --  110.00 -99.00 150.00   56
 60  \w     40.00  80.00   0.50    1.02    --  110.00 -99.00 120.00   80
 61  \w     46.00  76.00   0.50    1.02    --  110.00 -99.00 150.00   60
 62  \w    -61.00 -34.00   0.50    0.33    --  -49.87 -57.00 -90.00   54
 63  \w    -67.00 -42.00   0.50    0.33    --  -49.87 -19.00-120.00   50
 64  \w    -65.00 -37.00   0.50    0.33    --  -49.87 -38.00-180.00   56
 65  \w    -72.00 -46.00   0.50    1.02    --  -70.00 -77.00-180.00   52
 66  \w    -71.00 -46.00   0.50    1.02    --  -70.00 -77.00-150.00   50
 67  \w   -113.00 -73.00   0.50    0.33    --  -49.87 -19.00-120.00   80
 68  \w   -115.00 -86.00   0.50    0.33    --  -49.87 -38.00-180.00   58
 69  \w    -74.00 -46.00   0.50    1.02    --  -70.00 -78.00 -11.99   56
 70  \w    -72.00 -47.00   0.50    1.02    --  -70.00 -77.00   7.01   50
 71  \w    -79.00 -48.00   0.50    1.02    --  -70.00 -77.00  90.00   62
 72  \w    -74.00 -49.00   0.50    1.02    --  -70.00 -77.00 120.00   50
 73  \w    -73.00 -48.00   0.50    1.02    --  -70.00 -74.00 161.28   50
 74  \w    -84.00 -45.00   0.50    1.02    --  -70.00 -79.00  71.95   78
 75  \w    -77.00 -48.00   0.50    1.02    --  -70.00 -80.00  63.37   58
 76  \w   -136.00 -91.00   0.50    1.02    --  -70.00 -74.00 161.28   90
 77  \w    -91.00  -9.00   0.50    1.02    --  -70.00  79.00  71.00  164
 78  \w   -121.00 -74.00   0.50    0.33    --  -49.87 178.00 120.00   94
;
_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      0.0106740000
_diffrn_orient_matrix_UB_12      0.0941846000
_diffrn_orient_matrix_UB_13      0.1086668000
_diffrn_orient_matrix_UB_21      0.1450955000
_diffrn_orient_matrix_UB_22      -0.0228990000
_diffrn_orient_matrix_UB_23      0.0170233000
_diffrn_orient_matrix_UB_31      0.0161225000
_diffrn_orient_matrix_UB_32      0.1429382000
_diffrn_orient_matrix_UB_33      -0.0688417000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            26703
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.412
_diffrn_reflns_theta_min         4.200
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.514
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.797
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_description       plate
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.096
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         2432
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0449
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0641P)^2^+0.3261P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1157
_refine_ls_wR_factor_ref         0.1190
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2194
_reflns_number_total             2432
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00393_si_005.cif
_cod_data_source_block           bm230819_1_1
_cod_depositor_comments
'Adding full bibliography for 4517528--4517534.cif.'
_cod_database_code               4517534
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C14H19N
_diffrn_oxdiff_digest_frames
;
019e0aa0d3d6e07ee313b441c5258dd9d906268b90c
;
_diffrn_oxdiff_digest_hkl
;
0143107366c5e337b26ba8563444f55a6995b3
;
_reflns_odcompleteness_completeness 100.00
_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 C(H,H) groups, All N(H) groups
2. Restrained distances
 N1-H1
 0.93 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3B,H3A), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C10(H10A,H10B)
3.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14)
;
_shelx_res_checksum              15277
_shelx_hkl_checksum              6363
_olex2_date_sample_data_collection 2019-08-20
_olex2_date_sample_submission    2019-08-14
_olex2_submission_original_sample_id bm230819_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 2.001
_oxdiff_exptl_absorpt_empirical_full_min 0.768