Mild and Regioselective Pd(OAc)2-Catalyzed C–H Arylation of Tryptophans by [ArN2]X, Promoted by Tosic Acid
Reay, Alan J.; Hammarback, L. Anders; Bray, Joshua T. W.; Sheridan, Thomas; Turnbull, David; Whitwood, Adrian C.; Fairlamb, Ian J. S.; ACS Catalysis  (2017) 5174–; doi:10.1021/acscatal.6b03121

data_4514162
_publ_section_title
;
 Mild and Regioselective Pd(OAc)2-Catalyzed C--H Arylation of Tryptophans
 by [ArN2]X, Promoted by Tosic Acid
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              5174
_journal_paper_doi               10.1021/acscatal.6b03121
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H26 N2 O3'
_chemical_formula_sum            'C23 H26 N2 O3'
_chemical_formula_weight         378.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-12-01
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.507(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7152(3)
_cell_length_b                   13.5902(4)
_cell_length_c                   8.7625(3)
_cell_measurement_reflns_used    3894
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      70.7620
_cell_measurement_theta_min      10.2710
_cell_volume                     1020.44(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9990
_diffrn_measured_fraction_theta_max 0.9990
_diffrn_measurement_details
;
  1 omega   -2.00   25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  120.0000 27

  2 omega  -58.00  -31.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  -90.0000 27

  3 omega  -29.00   43.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000  -60.0000 72

  4 omega  -22.00   19.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  -90.0000 41

  5 omega  -15.00   78.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -19.0000 -120.0000 93

  6 omega   20.00  127.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   19.0000  -30.0000 107

  7 omega   -8.00   82.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -77.0000   90.0000 90

  8 omega  -17.00   40.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -37.0000    0.0000 57

  9 omega   25.00   51.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  -90.0000 26

 10 omega   69.00   96.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000 -125.0000  -90.0000 27

 11 omega   38.00  124.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000   30.0000 86

 12 omega   66.00  111.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  150.0000 45

 13 omega   72.00  107.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   60.0000 35

 14 omega   44.00   94.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -120.0000 50

 15 omega   87.00  119.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000 -120.0000 32

 16 omega   50.00   78.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000 -120.0000 28

 17 omega  120.00  175.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -150.0000 55

 18 omega   35.00   89.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000  -60.0000 54

 19 omega   45.00   77.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -37.0000 -180.0000 32

 20 omega   89.00  174.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000 -150.0000 85

 21 omega   42.00  103.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -50.0000   60.0000 61

 22 omega  141.00  177.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000   60.0000 36

 23 omega  144.00  174.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  -90.0000 30

 24 omega   90.00  134.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000   60.0000 44

 25 omega   86.00  115.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -90.0000 29

 26 omega   42.00  127.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000  -60.0000 85

 27 omega   99.00  177.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   37.0000  -90.0000 78

 28 omega  114.00  141.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  -90.0000 27

 29 omega   36.00  170.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   12.0000 -180.0000 134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0727338000
_diffrn_orient_matrix_UB_12      -0.0259487000
_diffrn_orient_matrix_UB_13      0.1689623000
_diffrn_orient_matrix_UB_21      0.0635651000
_diffrn_orient_matrix_UB_22      -0.0967750000
_diffrn_orient_matrix_UB_23      -0.0556658000
_diffrn_orient_matrix_UB_31      0.1515490000
_diffrn_orient_matrix_UB_32      0.0530049000
_diffrn_orient_matrix_UB_33      -0.0189676000
_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  0.0256
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            6691
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.058
_diffrn_reflns_theta_max         67.058
_diffrn_reflns_theta_min         5.134
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.655
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.940
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
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    1.232
_exptl_crystal_description       needle
_exptl_crystal_F_000             404
_exptl_crystal_size_max          0.2485
_exptl_crystal_size_mid          0.1431
_exptl_crystal_size_min          0.0656
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 1605 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.09(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         3634
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0359
_refine_ls_R_factor_gt           0.0342
_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^)+(0.0608P)^2^+0.0666P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0912
_reflns_Friedel_coverage         0.911
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3483
_reflns_number_total             3634
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b03121_si_002.cif
_cod_data_source_block           ijsf1488
_cod_database_code               4514162
_chemical_oxdiff_formula         'C23 H26 N2 O3'
_chemical_oxdiff_usercomment     'Alan AJR-5-402'
_reflns_odcompleteness_completeness 99.90
_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)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C14(H14), C16(H16)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              51801
_shelx_hkl_checksum              15206
_shelx_shelxl_version_number     2014/7