Site-specific indolation of proline-based peptides via copper(ii)-catalyzed oxidative coupling of tertiary amine N-oxides.
Wu, Xiaowei; Zhang, Dengyou; Zhou, Shengbin; Gao, Feng; Liu, Hong; Chemical communications (Cambridge, England) 51 (2015) 12571–12573; doi:10.1039/c5cc03706a

data_7117622
_publ_section_title
;
 Site-specific indolation of proline-based peptides via
 copper(ii)-catalyzed oxidative coupling of tertiary amine N-oxides.
;
_journal_issue                   63
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              12571
_journal_page_last               12573
_journal_paper_doi               10.1039/c5cc03706a
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C29 H37 N3 O3'
_chemical_formula_sum            'C29 H37 N3 O3'
_chemical_formula_weight         475.61
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2014-08-27
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2014-09-11 deposited with the CCDC.
2015-06-26 downloaded from the CCDC.
;
_cell_angle_alpha                89.715(3)
_cell_angle_beta                 77.329(3)
_cell_angle_gamma                77.339(3)
_cell_formula_units_Z            4
_cell_length_a                   13.8032(6)
_cell_length_b                   14.0849(6)
_cell_length_c                   14.8146(6)
_cell_measurement_reflns_used    3057
_cell_measurement_temperature    130
_cell_measurement_theta_max      61.87
_cell_measurement_theta_min      5.04
_cell_volume                     2738.9(2)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.949
_diffrn_measured_fraction_theta_max 0.918
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0705
_diffrn_reflns_av_unetI/netI     0.1017
_diffrn_reflns_Laue_measured_fraction_full 0.949
_diffrn_reflns_Laue_measured_fraction_max 0.918
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            23447
_diffrn_reflns_point_group_measured_fraction_full 0.648
_diffrn_reflns_point_group_measured_fraction_max 0.624
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.246
_diffrn_reflns_theta_min         5.035
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5511
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1422 before and 0.0688 after correction.
The Ratio of minimum to maximum transmission is 0.7316.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.153
_exptl_crystal_description       prism
_exptl_crystal_F_000             1024
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.761
_refine_diff_density_min         -0.328
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 1966 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(3)
_refine_ls_extinction_coef       0.0049(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1278
_refine_ls_number_reflns         13022
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0891
_refine_ls_R_factor_gt           0.0725
_refine_ls_shift/su_max          0.051
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1369P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1976
_refine_ls_wR_factor_ref         0.2174
_reflns_Friedel_coverage         0.361
_reflns_Friedel_fraction_full    0.347
_reflns_Friedel_fraction_max     0.331
_reflns_number_gt                10118
_reflns_number_total             13022
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5cc03706a2.cif
_cod_data_source_block           cu_dm14486_0m
_cod_database_code               7117622
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.866
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,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:
 C11(H11), C14(H14), C23(H23), C27(H27), C11B(H11B), C14B(H14B), C23B(H23B),
 C27B(H27B), C11A(H11A), C14A(H14A), C23A(H23A), C27A(H27A), C11C(H11C),
 C14C(H14C), C23C(H23C), C27C(H27C)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C12(H12A,H12B), C13(H13A,H13B), C15(H15A,H15B), C26(H26A,H26B),
 C2B(H2BA,H2BB), C12B(H12C,H12D), C13B(H13C,H13D), C15B(H15C,H15D), C26B(H26C,
 H26D), C2A(H2AA,H2AB), C12A(H12E,H12F), C13A(H13E,H13F), C15A(H15E,H15F),
 C26A(H26E,H26F), C2C(H2CA,H2CB), C12C(H12G,H12H), C13C(H13G,H13H), C15C(H15G,
 H15H), C26C(H26G,H26H)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), N7(H7), N9(H9), C4B(H4B), C5B(H5B), C6B(H6B),
 C10B(H10B), C17B(H17B), C18B(H18B), C19B(H19B), C20B(H20B), C21B(H21B),
 N4(H4A), N6(H6A), C4A(H4AA), C5A(H5A), C6A(H6AA), C10A(H10A), C17A(H17A),
 C18A(H18A), C19A(H19A), C20A(H20A), C21A(H21A), N10(H10C), N12(H12), C4C(H4C),
 C5C(H5C), C6C(H6C), C10C(H10D), C17C(H17C), C18C(H18C), C19C(H19C), C20C(H20C),
  C21C(H21C)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C25(H25A,H25B,H25C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C1B(H1BA,H1BB,H1BC), C25B(H25D,H25E,H25F), C28B(H28D,H28E,H28F),
 C29B(H29D,H29E,H29F), C1A(H1AA,H1AB,H1AC), C25A(H25G,H25H,H25I), C28A(H28G,
 H28H,H28I), C29A(H29G,H29H,H29I), C1C(H1CA,H1CB,H1CC), C25C(H25J,H25K,H25L),
 C28C(H28J,H28K,H28L), C29C(H29J,H29K,H29L)
;
_shelx_res_checksum              51829
_olex2_submission_special_instructions 'No special instructions were received'