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_4514163
_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         'C20 H19 Cl N2 O3'
_chemical_formula_sum            'C20 H19 Cl N2 O3'
_chemical_formula_weight         370.82
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3'
_symmetry_space_group_name_Hall  'R 3'
_symmetry_space_group_name_H-M   'R 3 :H'
_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                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   20.7806(2)
_cell_length_b                   20.7806(2)
_cell_length_c                   11.18107(13)
_cell_measurement_reflns_used    13099
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      70.8280
_cell_measurement_theta_min      4.2340
_cell_volume                     4181.48(7)
_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 1.0000
_diffrn_measured_fraction_theta_max 1.0000
_diffrn_measurement_details
;
  1 omega   -9.00   52.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000   90.0000 61

  2 omega    2.00   93.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -99.0000   30.0000 91

  3 omega   83.00  109.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   90.0000 26

  4 omega   65.00  109.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -30.0000 44

  5 omega   46.00  137.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -30.0000 91

  6 omega   82.00  108.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   37.0000    0.0000 26

  7 omega  114.00  176.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 62

  8 omega  132.00  169.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 37

  9 omega  140.00  173.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -150.0000 33

 10 omega  113.00  167.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 54

 11 omega  129.00  176.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 47

 12 omega  137.00  168.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 31

 13 omega  137.00  176.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 39

 14 omega  118.00  173.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 55

 15 omega  112.00  174.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 62

 16 omega  109.00  173.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -120.0000 64

 17 omega  108.00  173.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 65

 18 omega  100.00  126.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   74.0000 -173.4918 26

 19 omega   82.00  109.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   37.0000 -150.0000 27

 20 omega   87.00  163.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -120.0000 76

 21 omega   86.00  137.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -150.0000 51

 22 omega   86.00  126.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  -60.0000 40

 23 omega   79.00  120.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 41

 24 omega   79.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 25

 25 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 26

 26 omega   78.00  103.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 25

 27 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 26

 28 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 26

 29 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 26

 30 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 26

 31 omega   87.00  176.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000   60.0000 89

 32 omega   86.00  147.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  150.0000 61

 33 omega   80.00  126.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   75.0000  132.9707 46

 34 omega   81.00  112.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  162.1639 31

 35 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 26

 36 omega   86.00  145.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  120.0000 59

 37 omega   79.00  105.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 26

 38 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 26

 39 omega   83.00  119.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   37.0000  120.0000 36

 40 omega   78.00  104.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 26

 41 omega   82.00  109.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   37.0000   30.0000 27

 42 omega   82.00  128.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   37.0000   60.0000 46

 43 omega   81.00  120.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000  -30.0000 39

 44 omega   75.00  125.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000   17.6673 50

 45 omega   54.00  110.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   54.0000  -48.3021 56

 46 omega   32.00   58.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   75.0000  -72.1257 26

 47 omega   25.00   54.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000  -30.0000 29

 48 omega   26.00   54.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000   17.6673 28

 49 omega   32.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   74.0000   39.5521 31

 50 omega   34.00  121.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   73.0000   81.9921 87

 51 omega   32.00   63.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  162.1639 31

 52 omega   28.00   53.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   75.0000  132.9707 25

 53 omega   15.00   40.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   82.0000  149.1356 25

 54 omega    8.00   33.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   87.0000  126.9106 25

 55 omega   11.00   36.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   82.0000  108.2199 25

 56 omega    8.00   33.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   87.0000   26.2326 25

 57 omega   10.00   35.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   84.0000  -51.5840 25

 58 omega   25.00   51.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   77.0000  -90.0000 26

 59 omega   32.00  127.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   75.0000 -137.4673 95

 60 omega   35.00   61.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   74.0000 -173.4918 26

 61 omega    7.00   32.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   89.0000 -171.7669 25

 62 omega   -9.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000  -90.0000 75

 63 omega   17.00   65.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000   60.0000 48

 64 omega  -11.00   16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000  -60.0000 27

 65 omega    4.00   86.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -99.0000 -150.0000 82

 66 omega   53.00  112.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -180.0000 59

 67 omega   45.00  136.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -180.0000 91

 68 omega   -8.00   72.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -57.0000 -120.0000 80

 69 omega  -28.00   16.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000   60.0000 44

 70 omega  -36.00   -2.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       20.0000  123.0000   18.0388 34

 71 omega  -25.00    0.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       28.0000  118.0000  -86.6126 25

 72 omega  -34.00    4.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       12.0000  116.0000  175.3026 38

 73 omega  -63.00  -21.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000  -60.0000 42
;
_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      -0.0560911000
_diffrn_orient_matrix_UB_12      -0.0307113000
_diffrn_orient_matrix_UB_13      -0.1039413000
_diffrn_orient_matrix_UB_21      -0.0475462000
_diffrn_orient_matrix_UB_22      -0.0722423000
_diffrn_orient_matrix_UB_23      0.0708178000
_diffrn_orient_matrix_UB_31      -0.0438163000
_diffrn_orient_matrix_UB_32      0.0341389000
_diffrn_orient_matrix_UB_33      0.0562371000
_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  0.0214
_diffrn_reflns_av_unetI/netI     0.0128
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            19066
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.013
_diffrn_reflns_theta_max         67.013
_diffrn_reflns_theta_min         4.255
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.004
_exptl_absorpt_correction_T_max  0.986
_exptl_absorpt_correction_T_min  0.974
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1746
_exptl_crystal_size_max          0.183
_exptl_crystal_size_mid          0.1321
_exptl_crystal_size_min          0.0705
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 1613 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3300
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0219
_refine_ls_R_factor_gt           0.0217
_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^)+(0.0300P)^2^+2.5982P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0550
_refine_ls_wR_factor_ref         0.0552
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                3273
_reflns_number_total             3300
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs6b03121_si_002.cif
_cod_data_source_block           ijsf1487
_cod_original_cell_volume        4181.48(10)
_cod_database_code               4514163
_chemical_oxdiff_formula         'C20 H19 Cl N2 O3'
_chemical_oxdiff_usercomment     Alan-5-405
_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.a Ternary CH refined with riding coordinates:
 C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C13(H13), C14(H14)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              13277
_shelx_hkl_checksum              4696
_shelx_shelxl_version_number     2014/7