Pd-Catalyzed Site-Selective C(sp2)–H Radical Acylation of Phenylalanine Containing Peptides with Aldehydes
Correa, Arkaitz; San Segundo, Marcos; Chemical Science  (2019) –; doi:10.1039/C9SC03425K

data_1552166
_publ_section_title
;
 Pd-Catalyzed Site-Selective C(sp2)--H Radical Acylation of Phenylalanine
 Containing Peptides with Aldehydes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC03425K
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H13 Br2 Cl N2 O3'
_chemical_formula_sum            'C16 H13 Br2 Cl N2 O3'
_chemical_formula_weight         476.55
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-04-17T11:54:08-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_audit_update_record
;
2019-07-08 deposited with the CCDC.    2019-08-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.927(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.22428(16)
_cell_length_b                   13.92307(19)
_cell_length_c                   8.40898(16)
_cell_measurement_reflns_used    7774
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      74.097
_cell_measurement_theta_min      5.828
_cell_volume                     865.98(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2012
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_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    -12.00  83.00   1.00    1.00    --   42.13 -19.00   0.00   95
  2  \w     32.00 102.00   1.00    1.00    --   42.13  38.00   0.00   70
  3  \w     16.00 103.00   1.00    1.00    --   42.13  57.00-150.00   87
  4  \w     18.00  56.00   1.00    1.00    --   42.13  38.00 -30.00   38
  5  \w    -15.00  51.00   1.00    1.00    --   42.13 -77.00-180.00   66
  6  \w     47.00 112.00   1.00    1.00    --  107.93-125.00  60.00   65
  7  \w     52.00  87.00   1.00    1.00    --  107.93 -94.00  90.00   35
  8  \w     79.00 155.00   1.00    1.00    --  107.93  61.00  60.00   76
  9  \w     32.00  64.00   1.00    1.00    --  107.93 -30.00  30.00   32
 10  \w     82.00 155.00   1.00    1.00    --  107.93  45.00   0.00   73
 11  \w     35.00  77.00   1.00    1.00    --  107.93 -45.00  90.00   42
 12  \w     35.00  61.00   1.00    1.00    --  107.93 -45.00-120.00   26
 13  \w     36.00  66.00   1.00    1.00    --  107.93 -30.00 120.00   30
 14  \w     37.00  99.00   1.00    1.00    --  107.93 -94.00 -90.00   62
 15  \w     35.00  67.00   1.00    1.00    --  107.93 -30.00 -60.00   32
 16  \w     40.00  66.00   1.00    1.00    --  107.93 -30.00-120.00   26
 17  \w     32.00  57.00   1.00    1.00    --  107.93 -30.00  60.00   25
 18  \w     34.00  64.00   1.00    1.00    --  107.93 -30.00-180.00   30
 19  \w     38.00  63.00   1.00    1.00    --  107.93 -30.00 150.00   25
 20  \w     70.00 118.00   1.00    1.00    --  107.93-125.00-150.00   48
 21  \w     48.00  91.00   1.00    1.00    --  107.93 -94.00-150.00   43
 22  \w     73.00 154.00   1.00    1.00    --  107.93 125.00-180.00   81
 23  \w     48.00  93.00   1.00    1.00    --   42.13-125.00  60.00   45
 24  \w     12.00  38.00   1.00    1.00    --   42.13-125.00  60.00   26
 25  \w     32.00  57.00   1.00    1.00    --  107.93 -30.00 -30.00   25
 26  \w     34.00  81.00   1.00    1.00    --  107.93 -94.00 -30.00   47
 27  \w    107.00 142.00   1.00    1.00    --  107.93  45.00 -60.00   35
 28  \w     20.00  50.00   1.00    1.00    --  107.93   0.00 -90.00   30
 29  \w    -70.00  31.00   1.00    1.00    --  -42.13  57.00 -30.00  101
 30  \w   -118.00 -10.00   1.00    1.00    --  -42.13 -77.00  90.00  108
 31  \w   -118.00 -10.00   1.00    1.00    --  -42.13 -77.00 -30.00  108
 32  \w   -118.00 -10.00   1.00    1.00    --  -42.13 -77.00-150.00  108
 33  \w     10.00 118.00   1.00    1.00    --   42.13  77.00 120.00  108
 34  \w     14.00 115.00   1.00    1.00    --   42.13  57.00  90.00  101
;
_diffrn_measurement_device       'four-circle\k-geometry diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0744593
_diffrn_orient_matrix_UB_12      0.1019737
_diffrn_orient_matrix_UB_13      0.0041401
_diffrn_orient_matrix_UB_21      -0.1721142
_diffrn_orient_matrix_UB_22      0.026197
_diffrn_orient_matrix_UB_23      -0.1672409
_diffrn_orient_matrix_UB_31      -0.0906358
_diffrn_orient_matrix_UB_32      0.0340257
_diffrn_orient_matrix_UB_33      0.1162532
_diffrn_radiation_monochromator  'Multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       8
_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       -9
_diffrn_reflns_number            9363
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.958
_diffrn_reflns_theta_min         5.851
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    7.522
_exptl_absorpt_correction_T_max  0.655
_exptl_absorpt_correction_T_min  0.211
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
                        model based on expressions derived by R.C. Clark & J.S.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
        Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.828
_exptl_crystal_description       plate
_exptl_crystal_F_000             468
_exptl_crystal_size_max          0.427
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.094
_refine_diff_density_max         0.306
_refine_diff_density_min         -0.362
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 1414 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
 The Friedel pair coverage of the experiment is almost complete 
 (100%). Analysis of the absolute structure using likelihood methods
 (Hooft, Straver & Spek, 2008) was performed using PLATON
 (Spek, 2009). The resulting value was y=-0.005(107)
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3199
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0301
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0441P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.072
_refine_ls_wR_factor_ref         0.0727
_reflns_Friedel_coverage         0.913
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3134
_reflns_number_total             3199
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc03425k2.cif
_cod_data_source_block           a20190132_acn1250b
_cod_original_cell_volume        865.97(3)
_cod_database_code               1552166