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_4517529
_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         'C33 H56 Ni P2 S, C7 H8'
_chemical_formula_sum            'C40 H64 Ni P2 S'
_chemical_formula_weight         697.62
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0470(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.76550(10)
_cell_length_b                   14.09800(10)
_cell_length_c                   22.42550(10)
_cell_measurement_reflns_used    69505
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.3400
_cell_measurement_theta_min      3.6640
_cell_volume                     3714.46(4)
_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 1.000
_diffrn_measured_fraction_theta_max 0.994
_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    -97.00 -28.00   0.50    0.10    --  -26.00 163.00 -30.44  138
  2  \w    -89.00 -25.00   0.50    0.10    --  -26.00 152.00-107.68  128
  3  \w     -3.00  22.00   0.50    0.10    --   30.00  99.00  49.21   50
  4  \w     36.00  74.00   0.50    0.10    --   49.37  57.00 -60.00   76
  5  \w     34.00  80.00   0.50    0.10    --   49.37  57.00 120.00   92
  6  \w     26.00  58.00   0.50    0.10    --   49.37  77.00-150.00   64
  7  \w     96.00 121.00   0.50    0.10    --   49.37  57.00 120.00   50
  8  \w     26.00  52.00   0.50    0.10    --   49.37  77.00 -60.00   52
  9  \w     34.00  62.00   0.50    0.10    --   49.37  57.00 -90.00   56
 10  \w    -91.00 -37.00   0.50    0.10    --  -49.87 -38.00-120.00  108
 11  \w   -124.00 -37.00   0.50    0.10    --  -49.87 -38.00 -30.00  174
 12  \w     -9.00  25.00   0.50    0.10    --  -49.87  19.00 150.00   68
 13  \w     -6.00  21.00   0.50    0.10    --  -49.87  19.00-120.00   54
 14  \w    -71.00 -37.00   0.50    0.10    --  -49.87 -44.00-176.96   68
 15  \w   -124.00 -86.00   0.50    0.10    --  -49.87 -44.00-176.96   76
 16  \w   -123.00 -37.00   0.50    0.10    --  -49.87 -38.00  60.00  172
 17  \w     20.00  45.00   0.50    0.10    --   50.00  90.00  45.95   50
 18  \w     20.00  45.00   0.50    0.10    --   50.00  90.00 110.15   50
 19  \w     29.00  55.00   0.50    0.10    --   54.00  80.00  -2.06   52
 20  \w     28.00  55.00   0.50    0.10    --   54.00  82.00-167.54   54
 21  \w     93.00 123.00   0.50    0.10    --   58.00  82.00 -54.53   60
 22  \w     32.00  58.00   0.50    0.10    --   58.00  82.00 -54.53   52
 23  \w     40.00  66.00   0.50    0.10    --   66.00  82.00  -5.37   52
 24  \w    -68.00 -42.00   0.50    0.25    --  -66.00 -77.00-127.83   52
 25  \w    -81.00 -46.00   0.50    0.25    --  -70.00 -77.00  90.00   70
 26  \w     45.00  88.00   0.50    0.10    --   70.00  80.00  71.71   86
 27  \w     45.00  72.00   0.50    0.10    --   70.00  80.00  -1.17   54
 28  \w   -131.00-105.00   0.50    0.25    --  -70.00 -77.00  90.00   52
 29  \w    -91.00 -10.00   0.50    0.25    --  -70.00 125.00 150.00  162
 30  \w    -92.00 -48.00   0.50    0.25    --  -70.00 -78.00-158.85   88
 31  \w    -73.00 -46.00   0.50    0.25    --  -70.00 -79.00 -67.12   54
 32  \w   -133.00 -43.00   0.50    0.25    --  -70.00 -83.00 150.64  180
 33  \w    -73.00 -43.00   0.50    0.25    --  -70.00 -83.00 -17.49   60
 34  \w    -75.00 -46.00   0.50    0.25    --  -70.00 -77.00-180.00   58
 35  \w    -69.00 -44.00   0.50    0.25    --  -70.00 -82.00 120.44   50
 36  \w   -137.00-112.00   0.50    0.25    --  -70.00 -82.00 120.44   50
 37  \w    -72.00 -46.00   0.50    0.25    --  -70.00 -77.00 -90.00   52
 38  \w    -74.00 -48.00   0.50    0.25    --  -70.00 -74.00 152.30   52
 39  \w    -84.00 -45.00   0.50    0.25    --  -70.00 -79.00  72.62   78
 40  \w    -95.00 -45.00   0.50    0.25    --  -70.00 -79.00-131.36  100
 41  \w     50.00  90.00   0.50    0.10    --   74.00  77.00-119.32   80
 42  \w     50.00  88.00   0.50    0.10    --   74.00  78.00 -34.74   76
 43  \w    112.00 138.00   0.50    0.10    --   74.00  79.00 -69.77   52
 44  \w     50.00  76.00   0.50    0.10    --   74.00  79.00 -69.77   52
 45  \w     50.00  82.00   0.50    0.10    --   74.00  79.00  33.35   64
 46  \w    100.00 138.00   0.50    0.10    --   74.00  77.00-119.32   76
 47  \w     62.00 105.00   0.50    0.25    --   82.00  69.00  30.00   86
 48  \w     65.00 120.00   0.50    0.25    --   86.00  71.00 162.40  110
 49  \w     42.00 109.00   0.50    0.25    --  110.00 -99.00  60.00  134
 50  \w     98.00 129.00   0.50    0.25    --  110.00  38.00   0.00   62
 51  \w     86.00 113.00   0.50    0.25    --  110.00  77.00 -30.00   54
 52  \w     59.00 117.00   0.50    0.25    --  110.00-125.00 -30.00  116
 53  \w     97.00 123.00   0.50    0.25    --  110.00  57.00-150.00   52
 54  \w     86.00 175.00   0.50    0.25    --  110.00  77.00 -60.00  178
 55  \w     94.00 132.00   0.50    0.25    --  110.00 -77.00  90.00   76
 56  \w     38.00  68.00   0.50    0.25    --  110.00 -57.00-150.00   60
 57  \w     50.00  79.00   0.50    0.25    --  110.00 -77.00  90.00   58
 58  \w    116.00 176.00   0.50    0.25    --  110.00  77.00 -30.00  120
 59  \w     45.00 110.00   0.50    0.25    --  110.00 -99.00 150.00  130
 60  \w     92.00 134.00   0.50    0.25    --  110.00 -77.00 -60.00   84
 61  \w     86.00 137.00   0.50    0.25    --  110.00  77.00-150.00  102
 62  \w    140.00 176.00   0.50    0.25    --  110.00  77.00-150.00   72
 63  \w     46.00  85.00   0.50    0.25    --  110.00 -77.00 -60.00   78
 64  \w    138.00 175.00   0.50    0.25    --  110.00  77.00  90.00   74
 65  \w     86.00 134.00   0.50    0.25    --  110.00  77.00  90.00   96
 66  \w     89.00 173.00   0.50    0.25    --  110.00  70.00 154.77  168
 67  \w     82.00 117.00   0.50    0.25    --  110.00-125.00  90.00   70
 68  \w     86.00 165.00   0.50    0.25    --  110.00  77.00   0.00  158
 69  \w     98.00 124.00   0.50    0.25    --  110.00  38.00  90.00   52
 70  \w     98.00 124.00   0.50    0.25    --  110.00  38.00-150.00   52
 71  \w    119.00 174.00   0.50    0.25    --  110.00  77.00  30.00  110
 72  \w     86.00 112.00   0.50    0.25    --  110.00  77.00  30.00   52
 73  \w     98.00 127.00   0.50    0.25    --  110.00  38.00 -60.00   58
 74  \w    101.00 178.00   0.50    0.25    --  110.00 125.00 120.00  154
 75  \w     97.00 145.00   0.50    0.25    --  110.00  57.00-120.00   96
 76  \w    117.00 176.00   0.50    0.25    --  110.00  77.00 -90.00  118
 77  \w    122.00 174.00   0.50    0.25    --  110.00  77.00-180.00  104
 78  \w     86.00 115.00   0.50    0.25    --  110.00  77.00 -90.00   58
 79  \w    127.00 169.00   0.50    0.25    --  110.00  77.00-120.00   84
 80  \w     86.00 112.00   0.50    0.25    --  110.00  77.00-180.00   52
 81  \w     87.00 114.00   0.50    0.25    --  110.00  77.00-120.00   54
 82  \w     49.00  93.00   0.50    0.25    --  110.00 -99.00-120.00   88
 83  \w     98.00 156.00   0.50    0.25    --  110.00  38.00 120.00  116
 84  \w     97.00 167.00   0.50    0.25    --  110.00  57.00 120.00  140
 85  \w    122.00 175.00   0.50    0.25    --  110.00  77.00  60.00  106
 86  \w     86.00 111.00   0.50    0.25    --  110.00  77.00  60.00   50
 87  \w     98.00 145.00   0.50    0.25    --  110.00  38.00  60.00   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      -0.0234037000
_diffrn_orient_matrix_UB_12      0.0066756000
_diffrn_orient_matrix_UB_13      0.0668060000
_diffrn_orient_matrix_UB_21      0.0700456000
_diffrn_orient_matrix_UB_22      -0.0909161000
_diffrn_orient_matrix_UB_23      0.0121756000
_diffrn_orient_matrix_UB_31      0.1083497000
_diffrn_orient_matrix_UB_32      0.0602582000
_diffrn_orient_matrix_UB_33      0.0110209000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            102174
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.750
_diffrn_reflns_theta_min         3.705
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.275
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.587
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.247
_exptl_crystal_description       block
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.163
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.133
_refine_diff_density_max         0.424
_refine_diff_density_min         -0.297
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         8025
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0311
_refine_ls_R_factor_gt           0.0296
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0453P)^2^+1.4965P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0801
_refine_ls_wR_factor_ref         0.0811
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7581
_reflns_number_total             8025
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00393_si_008.cif
_cod_data_source_block           bm280919_1_1
_cod_depositor_comments
'Adding full bibliography for 4517528--4517534.cif.'
_cod_database_code               4517529
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C33H56NiP2S
_diffrn_oxdiff_digest_frames
;
01bc60631ac396646d7f1da571bc7fb52907270eebe
;
_diffrn_oxdiff_digest_hkl
;
0176157f308999037ccfada2c57f2268382a7a
;
_reflns_odcompleteness_completeness 99.99
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10), C16(H16), C22(H22), C28(H28)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
  C20(H20A,H20B), C21(H21A,H21B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,
 H25B), C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B),
 C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C3A(H3AA), C4A(H4A), C5A(H5A),
 C6A(H6A), C7A(H7A)
2.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              83180
_shelx_hkl_checksum              99502
_olex2_submission_original_sample_id bm280919_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 1.487
_oxdiff_exptl_absorpt_empirical_full_min 0.789