Decarboxylative Ritter-Type Amination by Cooperative Iodine (I/III)─Boron Lewis Acid Catalysis
Narobe, Rok; Murugesan, Kathiravan; Schmid, Simon; König, Burkhard; ACS Catalysis  (2021) 809–817; doi:10.1021/acscatal.1c05077

data_4519223
_publ_section_title
;
 Decarboxylative Ritter-Type Amination by Cooperative Iodine
 (I/III)&#x2500;Boron Lewis Acid Catalysis
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              809
_journal_page_last               817
_journal_paper_doi               10.1021/acscatal.1c05077
_journal_year                    2021
_chemical_formula_moiety         'C16 H16 F N O'
_chemical_formula_sum            'C16 H16 F N O'
_chemical_formula_weight         257.30
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-15
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.8690(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1669(2)
_cell_length_b                   12.9806(2)
_cell_length_c                   9.59280(10)
_cell_measurement_reflns_used    13729
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      66.7200
_cell_measurement_theta_min      5.2950
_cell_volume                     1349.97(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -80.00 -55.00   1.00    1.90    --  -43.66 115.00  57.00   25
  2  \w   -113.00 -88.00   1.00    1.90    --  -43.66 169.00-158.00   25
  3  \w     72.00  97.00   1.00    1.90    --   43.66 169.00-158.00   25
  4  \w     50.00  75.00   1.00    1.90    --   43.66-169.00-175.00   25
  5  \w      1.00  54.00   1.00    1.90    --   43.66-115.00 -32.00   53
  6  \w     50.00  75.00   1.00    8.00    --   86.50-169.00-175.00   25
  7  \w     95.00 120.00   1.00    8.00    --   86.50 115.00  57.00   25
  8  \w   -108.00 -69.00   1.00    8.00    --  -90.00 115.00  57.00   39
  9  \w   -134.00-109.00   1.00    8.00    --  -90.00-115.00 -32.00   25
 10  \w   -122.00 -97.00   1.00    8.00    --  -90.00 169.00-158.00   25
 11  \w    -88.00 -61.00   1.00    1.90    --  -43.66 -37.00   0.00   27
 12  \w     28.00 114.00   1.00    1.90    --   43.66  37.00  30.00   86
 13  \w     48.00  85.00   1.00    1.90    --   43.66  57.00-180.00   37
 14  \w     18.00 104.00   1.00    1.90    --   43.66  57.00 120.00   86
 15  \w   -162.00-135.00   1.00    8.00    --  -90.00 -77.00 -90.00   27
 16  \w   -148.00 -98.00   1.00    8.00    --  -90.00-125.00   0.00   50
 17  \w   -137.00-110.00   1.00    8.00    --  -90.00 -53.00 -25.60   27
 18  \w   -135.00-107.00   1.00    8.00    --  -90.00 160.00-123.03   28
 19  \w   -156.00 -63.00   1.00    8.00    --  -90.00 -30.00 -90.00   93
 20  \w   -100.00 -67.00   1.00    8.00    --  -90.00 -53.00  64.89   33
 21  \w    -82.00 -29.00   1.00    8.00    --  -90.00 125.00  60.00   53
 22  \w   -116.00 -20.00   1.00    8.00    --  -90.00  61.00  30.00   96
 23  \w    -97.00 -44.00   1.00    8.00    --  -90.00 108.00-111.93   53
 24  \w   -172.00-115.00   1.00    8.00    --  -90.00 -94.00 -90.00   57
 25  \w   -137.00-110.00   1.00    8.00    --  -90.00-125.00-120.00   27
 26  \w   -102.00 -17.00   1.00    8.00    --  -90.00  77.00  60.00   85
 27  \w   -161.00-127.00   1.00    8.00    --  -90.00 -77.00 -60.00   34
 28  \w   -159.00 -83.00   1.00    8.00    --  -90.00 -61.00   0.00   76
 29  \w   -156.00-117.00   1.00    8.00    --  -90.00 -63.00-144.70   39
 30  \w    -73.00 -46.00   1.00    8.00    --  -90.00 160.00-123.03   27
 31  \w   -110.00 -67.00   1.00    8.00    --  -90.00  88.00  85.46   43
 32  \w    -75.00 -48.00   1.00    8.00    --  -90.00 125.00-120.00   27
 33  \w   -104.00 -79.00   1.00    8.00    --  -90.00 125.00 120.00   25
 34  \w   -102.00 -65.00   1.00    8.00    --  -90.00 125.00-180.00   37
 35  \w   -110.00 -84.00   1.00    8.00    --  -90.00 125.00 -90.00   26
 36  \w    -87.00 -60.00   1.00    8.00    --  -90.00 125.00 -30.00   27
 37  \w   -100.00 -72.00   1.00    8.00    --  -90.00 125.00  30.00   28
 38  \w   -120.00 -85.00   1.00    8.00    --  -90.00 134.00-161.18   35
 39  \w   -109.00 -79.00   1.00    8.00    --  -90.00 112.00 127.34   30
 40  \w   -138.00 -67.00   1.00    8.00    --  -90.00 -50.00-126.23   71
 41  \w   -115.00 -33.00   1.00    8.00    --  -90.00 128.00 125.01   82
 42  \w   -146.00-105.00   1.00    8.00    --  -90.00 -94.00  30.00   41
 43  \w    -99.00 -68.00   1.00    8.00    --  -90.00 -63.00-144.70   31
 44  \w   -162.00-135.00   1.00    8.00    --  -90.00 -30.00  30.00   27
 45  \w   -124.00 -65.00   1.00    8.00    --  -90.00 -30.00  30.00   59
 46  \w   -105.00 -74.00   1.00    8.00    --  -90.00  92.00 -31.80   31
 47  \w   -148.00-121.00   1.00    8.00    --  -90.00 -71.00  80.05   27
 48  \w   -100.00 -51.00   1.00    8.00    --  -90.00  86.00 176.39   49
 49  \w   -144.00-104.00   1.00    8.00    --  -90.00 -77.00-120.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dualflex, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0329713000
_diffrn_orient_matrix_UB_12      0.1139869000
_diffrn_orient_matrix_UB_13      0.0338740000
_diffrn_orient_matrix_UB_21      -0.1381344000
_diffrn_orient_matrix_UB_22      0.0265226000
_diffrn_orient_matrix_UB_23      -0.0271493000
_diffrn_orient_matrix_UB_31      0.0048346000
_diffrn_orient_matrix_UB_32      -0.0197096000
_diffrn_orient_matrix_UB_33      0.1596356000
_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  0.0334
_diffrn_reflns_av_unetI/netI     0.0147
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            19662
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.860
_diffrn_reflns_theta_max         66.860
_diffrn_reflns_theta_min         4.078
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.718
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.837
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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            colourless
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       prism
_exptl_crystal_F_000             544
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.873
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     174
_refine_ls_number_reflns         2400
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0700P)^2^+0.6023P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2267
_reflns_number_total             2400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05077_si_004.cif
_cod_data_source_block           u040
_cod_database_code               4519223
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C16 H16 F N O'
_chemical_oxdiff_usercomment     Narobe_Koenig_RN-609-B
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.797
_reflns_odcompleteness_completeness 99.37
_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.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C6(H6), C16(H16), C15(H15), C10(H10), C14(H14), C11(H11), C13(H13),
 C12(H12)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              4343
_shelx_hkl_checksum              69421
_olex2_date_sample_data_collection 2021-04-13
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.786
_oxdiff_exptl_absorpt_empirical_full_min 0.719