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_4517533
_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         'C32 H53 Br Ni P2, C4 H8 O'
_chemical_formula_sum            'C36 H61 Br Ni O P2'
_chemical_formula_weight         710.40
_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             2019-10-21
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.2920(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.56520(10)
_cell_length_b                   22.46960(10)
_cell_length_c                   15.30990(10)
_cell_measurement_reflns_used    29418
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.3110
_cell_measurement_theta_min      3.9200
_cell_volume                     3505.82(5)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_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 0.990
_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    -23.00   9.00   0.50    0.73    --   49.37 -19.00 -30.00   64
  2  \w     74.00 104.00   0.50    2.70    --  110.00 -99.00  90.00   60
  3  \w     77.00 134.00   0.50    2.70    --  110.00 -77.00 150.00  114
  4  \w     71.00  98.00   0.50    2.70    --  110.00-125.00 120.00   54
  5  \w     50.00  76.00   0.50    2.70    --  110.00 -99.00 150.00   52
  6  \w     38.00  65.00   0.50    2.70    --  110.00 -57.00 120.00   54
  7  \w     38.00  65.00   0.50    2.70    --  110.00 -57.00  60.00   54
  8  \w     42.00  67.00   0.50    2.70    --  110.00 -57.00  30.00   50
  9  \w     38.00  67.00   0.50    2.70    --  110.00 -57.00  90.00   58
 10  \w     40.00  65.00   0.50    2.70    --  110.00 -57.00 150.00   50
 11  \w     49.00 117.00   0.50    2.70    --  110.00-125.00  60.00  136
 12  \w     85.00 117.00   0.50    2.70    --  110.00-125.00 -60.00   64
 13  \w     71.00 117.00   0.50    2.70    --  110.00-125.00-150.00   92
 14  \w     40.00  65.00   0.50    2.70    --  110.00 -57.00-150.00   50
 15  \w     38.00  68.00   0.50    2.70    --  110.00 -57.00 -90.00   60
 16  \w     39.00  64.00   0.50    2.70    --  110.00 -57.00 -60.00   50
 17  \w     44.00  69.00   0.50    2.70    --  110.00-125.00-150.00   50
 18  \w     41.00  68.00   0.50    2.70    --  110.00 -57.00-180.00   54
 19  \w    110.00 178.00   0.50    2.70    --  110.00  38.00 -60.00  136
 20  \w    139.00 178.00   0.50    2.70    --  110.00  38.00   0.00   78
 21  \w    112.00 177.00   0.50    2.70    --  110.00  57.00  60.00  130
 22  \w    144.00 170.00   0.50    2.70    --  110.00  57.00 120.00   52
 23  \w    149.00 176.00   0.50    2.70    --  110.00 125.00  90.00   54
 24  \w    139.00 164.00   0.50    2.70    --  110.00 125.00  60.00   50
 25  \w    102.00 127.00   0.50    2.70    --  110.00 125.00  90.00   50
 26  \w     95.00 124.00   0.50    2.70    --  110.00 125.00  60.00   58
 27  \w     94.00 177.00   0.50    2.70    --  110.00  57.00 -30.00  166
 28  \w    145.00 174.00   0.50    2.70    --  110.00  57.00-120.00   58
 29  \w     94.00 174.00   0.50    2.70    --  110.00  57.00 -90.00  160
 30  \w     94.00 134.00   0.50    2.70    --  110.00  57.00-120.00   80
 31  \w     74.00 117.00   0.50    0.73    --   49.37 178.00 -60.00   86
 32  \w     95.00 132.00   0.50    2.70    --  110.00  57.00 120.00   74
 33  \w     41.00  66.00   0.50    2.70    --  110.00-125.00 120.00   50
 34  \w    -25.00   8.00   0.50    0.73    --   49.37 -19.00 150.00   66
 35  \w     -8.00  26.00   0.50    0.73    --  -49.87  19.00 -60.00   68
 36  \w     -4.00  23.00   0.50    0.73    --  -49.87  19.00  30.00   54
 37  \w     -9.00  26.00   0.50    0.73    --  -49.87  19.00  60.00   70
 38  \w      0.00  26.00   0.50    0.73    --  -49.87  19.00 150.00   52
 39  \w    -63.00  17.00   0.50    0.73    --  -49.87  57.00 120.00  160
 40  \w    -36.00 -11.00   0.50    2.70    --  -70.00  38.00 -60.00   50
 41  \w    -38.00 -13.00   0.50    2.70    --  -70.00  38.00 -90.00   50
 42  \w    -25.00   1.00   0.50    2.70    --  -70.00  38.00-150.00   52
 43  \w    -89.00 -58.00   0.50    2.70    --  -70.00 -38.00 -90.00   62
 44  \w   -124.00 -46.00   0.50    0.73    --  -49.87 -38.00   0.00  156
 45  \w   -134.00 -97.00   0.50    2.70    --  -70.00 -99.00-180.00   74
 46  \w   -145.00-120.00   0.50    2.70    --  -70.00 -38.00 -90.00   50
 47  \w   -140.00-114.00   0.50    2.70    --  -70.00 -99.00  90.00   52
 48  \w    -87.00 -25.00   0.50    2.70    --  -70.00 125.00   0.00  124
;
_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      -0.0360453000
_diffrn_orient_matrix_UB_12      0.0637202000
_diffrn_orient_matrix_UB_13      0.0218280000
_diffrn_orient_matrix_UB_21      0.0200625000
_diffrn_orient_matrix_UB_22      -0.0175970000
_diffrn_orient_matrix_UB_23      0.1000109000
_diffrn_orient_matrix_UB_31      0.1453581000
_diffrn_orient_matrix_UB_32      0.0182272000
_diffrn_orient_matrix_UB_33      0.0200864000
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            48346
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.696
_diffrn_reflns_theta_min         3.581
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.183
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.814
_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 dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.346
_exptl_crystal_description       block
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.084
_exptl_crystal_size_mid          0.054
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.492
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         7560
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0239
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0300P)^2^+1.5450P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0608
_refine_ls_wR_factor_ref         0.0622
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6892
_reflns_number_total             7560
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00393_si_004.cif
_cod_data_source_block           bm191019_1_1
_cod_depositor_comments
'Adding full bibliography for 4517528--4517534.cif.'
_cod_database_code               4517533
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C36H61BrNiOP2
_reflns_odcompleteness_completeness 99.98
_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
2. Restrained distances
 O1A-C1A \\sim O1A-C4A \\sim O1B-C1B \\sim O1B-C4B
 with sigma of 0.02
 C2A-C1A \\sim C4A-C3A \\sim C2B-C1B \\sim C4B-C3B
 with sigma of 0.02
 C3A-C2A \\sim C3B-C2B
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 O1A, C1A, C2A, C3A, C4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1B, C1B, C2B, C3B, C4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(O1B)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(C3B)=
 Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=1-FVAR(1)
 Sof(O1A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=
 Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C9(H9), C15(H15), C21(H21), C27(H27)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B),
  C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,
 H24B), C25(H25A,H25B), C26(H26A,H26B), C28(H28A,H28B), C29(H29A,H29B),
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C1A(H1AA,H1AB), C2A(H2AA,H2AB),
  C3A(H3AA,H3AB), C4A(H4AA,H4AB), C1B(H1BA,H1BB), C2B(H2BA,H2BB), C3B(H3BA,
 H3BB), C4B(H4BA,H4BB)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8)
;
_shelx_res_checksum              33858
_shelx_hkl_checksum              38265
_olex2_date_sample_data_collection 2019-10-16
_olex2_date_sample_submission    2019-10-16
_olex2_submission_original_sample_id bm191019_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 1.544
_oxdiff_exptl_absorpt_empirical_full_min 0.829