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_4517531
_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         'C26 H48 Br2 Ni P2, C7 H8'
_chemical_formula_sum            'C33 H56 Br2 Ni P2'
_chemical_formula_weight         733.24
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.0520(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.22030(10)
_cell_length_b                   18.68700(10)
_cell_length_c                   15.28660(10)
_cell_measurement_reflns_used    32864
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.1690
_cell_measurement_theta_min      3.0830
_cell_volume                     3447.38(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 0.986
_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    -20.00   5.00   0.50    0.10    --   49.37 -19.00   0.00   50
  2  \w    -25.00   0.00   0.50    0.10    --   49.37 -19.00 150.00   50
  3  \w     -1.00  25.00   0.50    0.10    --  -49.87  19.00-180.00   52
  4  \w   -112.00 -34.00   0.50    0.10    --  -49.87 -77.00-150.00  156
  5  \w    -30.00  -4.00   0.50    0.10    --  -49.87  77.00  90.00   52
  6  \w    -72.00 -43.00   0.50    0.10    --  -49.87  77.00  90.00   58
  7  \w     -5.00  26.00   0.50    0.10    --  -49.87  19.00 -90.00   62
  8  \w     -8.00  22.00   0.50    0.10    --  -49.87  19.00 -60.00   60
  9  \w     -4.00  21.00   0.50    0.10    --  -49.87  19.00 -30.00   50
 10  \w     -5.00  20.00   0.50    0.10    --  -49.87  19.00-120.00   50
 11  \w     -9.00  16.00   0.50    0.10    --  -49.87  19.00  60.00   50
 12  \w     -8.00  23.00   0.50    0.10    --  -49.87  19.00   0.00   62
 13  \w   -139.00 -99.00   0.50    0.25    --  -70.00 -38.00-150.00   80
 14  \w   -137.00 -85.00   0.50    0.25    --  -70.00 -99.00-150.00  104
 15  \w    -31.00   0.00   0.50    0.25    --  -70.00  38.00 -30.00   62
 16  \w    -84.00 -24.00   0.50    0.25    --  -70.00 125.00-150.00  120
 17  \w    -35.00  -1.00   0.50    0.25    --  -70.00  38.00-120.00   68
 18  \w   -125.00 -92.00   0.50    0.25    --  -70.00 -77.00  90.00   66
 19  \w    -86.00 -61.00   0.50    0.25    --  -70.00 -38.00-150.00   50
 20  \w    -89.00 -47.00   0.50    0.25    --  -70.00 -77.00  90.00   84
 21  \w     40.00  65.00   0.50    0.25    --  110.00 -99.00 -30.00   50
 22  \w     45.00  71.00   0.50    0.25    --  110.00 -99.00 120.00   52
 23  \w     38.00  63.00   0.50    0.25    --  110.00 -57.00-180.00   50
 24  \w     39.00  64.00   0.50    0.25    --  110.00 -57.00  30.00   50
 25  \w    122.00 171.00   0.50    0.25    --  110.00  19.00-180.00   98
 26  \w     94.00 174.00   0.50    0.25    --  110.00  57.00 120.00  160
 27  \w     99.00 176.00   0.50    0.25    --  110.00  38.00  90.00  154
 28  \w     81.00 106.00   0.50    0.25    --  110.00 -99.00 120.00   50
 29  \w     40.00  68.00   0.50    0.25    --  110.00 -57.00 -30.00   56
 30  \w     40.00  87.00   0.50    0.25    --  110.00-125.00  60.00   94
 31  \w     38.00  64.00   0.50    0.25    --  110.00 -57.00-120.00   52
 32  \w     42.00  67.00   0.50    0.25    --  110.00 -57.00 -60.00   50
 33  \w     86.00 174.00   0.50    0.25    --  110.00  77.00   0.00  176
 34  \w     86.00 175.00   0.50    0.25    --  110.00  77.00-180.00  178
 35  \w    107.00 174.00   0.50    0.25    --  110.00 125.00  60.00  134
 36  \w    120.00 175.00   0.50    0.25    --  110.00  19.00 150.00  110
 37  \w     39.00  65.00   0.50    0.25    --  110.00 -57.00  60.00   52
 38  \w     43.00  93.00   0.50    0.25    --  110.00 -99.00  60.00  100
 39  \w    117.00 165.00   0.50    0.25    --  110.00  77.00 -60.00   96
 40  \w     42.00 103.00   0.50    0.25    --  110.00 -99.00-180.00  122
 41  \w    143.00 175.00   0.50    0.25    --  110.00  19.00 -90.00   64
 42  \w     73.00 108.00   0.50    0.25    --  110.00 -99.00 -30.00   70
 43  \w     98.00 124.00   0.50    0.25    --  110.00  19.00  90.00   52
 44  \w    148.00 174.00   0.50    0.25    --  110.00  19.00-150.00   52
 45  \w     55.00 117.00   0.50    0.25    --  110.00-125.00 -60.00  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      0.0056814000
_diffrn_orient_matrix_UB_12      0.0709478000
_diffrn_orient_matrix_UB_13      -0.0504574000
_diffrn_orient_matrix_UB_21      0.1272725000
_diffrn_orient_matrix_UB_22      -0.0059682000
_diffrn_orient_matrix_UB_23      0.0125003000
_diffrn_orient_matrix_UB_31      -0.0085701000
_diffrn_orient_matrix_UB_32      -0.0415608000
_diffrn_orient_matrix_UB_33      -0.0877975000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0410
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            48527
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.675
_diffrn_reflns_theta_min         3.663
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.539
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.483
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.413
_exptl_crystal_description       block
_exptl_crystal_F_000             1528
_exptl_crystal_size_max          0.226
_exptl_crystal_size_mid          0.194
_exptl_crystal_size_min          0.083
_refine_diff_density_max         1.054
_refine_diff_density_min         -1.246
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     414
_refine_ls_number_reflns         7400
_refine_ls_number_restraints     287
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0515
_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^)+(0.0602P)^2^+9.7186P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1362
_refine_ls_wR_factor_ref         0.1379
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6965
_reflns_number_total             7400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00393_si_006.cif
_cod_data_source_block           bm240919_2_1
_cod_depositor_comments
'Adding full bibliography for 4517528--4517534.cif.'
_cod_database_code               4517531
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C33H56Br2NiP2
_diffrn_oxdiff_digest_frames
;
01c47f98725f1db66416ac922b7b6d704e036324cc4
;
_diffrn_oxdiff_digest_hkl
;
012ca58ebfb88f9797889dc0e2cfd5c81ebad0
;
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2B-C1B = C2A-C1A
 1.52 with sigma of 0.01
 Br1A-Ni1 \\sim Br1-Ni1 \\sim Br2A-Ni1 \\sim Br2-Ni1
 with sigma of 0.02
 C2A-C1A \\sim C2B-C1B
 with sigma of 0.02
 C7A-C2A \\sim C3A-C2A \\sim C7A-C6A \\sim C4A-C3A \\sim C6A-C5A \\sim C5A-C4A
\\sim C3B-C2B \\sim C7B-C2B
 \\sim C4B-C3B \\sim C7B-C6B \\sim C5B-C4B \\sim C6B-C5B
 with sigma of 0.02
 C3A-C6A \\sim C4A-C7A \\sim C3B-C6B \\sim C4B-C7B
 with sigma of 0.02
 C3A-C7A \\sim C4A-C6A \\sim C3B-C7B \\sim C4B-C6B
 with sigma of 0.02
3. Restrained planarity
 C2A, C6A, C7A, C3A, C5A, C4A, C1A
 with sigma of 0.1
 C1B, C2B, C3B, C4B, C5B, C6B, C7B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C2A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C1A)
\\sim Ueq, Uanis(C6A) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C5A) \\sim Ueq,
Uanis(C2B) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C3B) \\sim Ueq, Uanis(C7B)
\\sim Ueq, Uanis(C4B) \\sim Ueq, Uanis(C6B) \\sim Ueq, Uanis(C5B) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Br2) = Uanis(Br2A)
Uanis(Br1) = Uanis(Br1A)
5. Rigid body (RIGU) restrains
 Ni1, Br1A, Br1, Br2, Br2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C2A, C7A, C3A, C6A, C4A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1B, C2B, C3B, C7B, C4B, C6B, C5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=
 Sof(H4BA)=Sof(C5B)=Sof(H5BA)=Sof(C6B)=Sof(H6BA)=Sof(C7B)=Sof(H7BA)=1-FVAR(1)
 Sof(C2A)=Sof(C6A)=Sof(H6AA)=Sof(C7A)=Sof(H7AA)=Sof(C3A)=Sof(H3A)=Sof(C5A)=
 Sof(H5AA)=Sof(C4A)=Sof(H4AA)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=FVAR(1)
 Sof(Br2A)=Sof(Br1A)=1-FVAR(2)
 Sof(Br1)=Sof(Br2)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C21(H21), C3(H3), C9(H9), C15(H15)
7.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C1(H1A,H1B), C2(H2A,H2B), C26(H26A,H26B), C14(H14A,H14B),
 C10(H10A,H10B), C8(H8A,H8B), C22(H22A,H22B), C6(H6A,H6B), C5(H5A,H5B),
 C24(H24A,H24B), C25(H25A,H25B), C23(H23A,H23B), C20(H20A,H20B), C7(H7A,H7B),
 C12(H12A,H12B), C16(H16A,H16B), C11(H11A,H11B), C13(H13A,H13B), C19(H19A,H19B),
  C18(H18A,H18B), C17(H17A,H17B)
7.c Me refined with riding coordinates:
 C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC)
7.d Aromatic/amide H refined with riding coordinates:
 C6A(H6AA), C7A(H7AA), C3A(H3A), C5A(H5AA), C4A(H4AA), C3B(H3B), C4B(H4BA),
 C5B(H5BA), C6B(H6BA), C7B(H7BA)
;
_shelx_res_checksum              18122
_shelx_hkl_checksum              1395
_olex2_date_sample_data_collection 2019-09-25
_olex2_date_sample_submission    2019-09-25
_olex2_submission_original_sample_id bm240919_2_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 1.334
_oxdiff_exptl_absorpt_empirical_full_min 0.851