Enantioselective synthesis of 3a-azido-pyrroloindolines by copper-catalyzed asymmetric dearomative azidation of tryptamines.
Lin, Cheng-Zhou; Jiang, Ling-Feng; Zhang, Guang-Yi; Zhou, Fang-Shuai; Wu, Shao-Hua; Cao, Jing; Deng, Qing-Hai; Chemical communications (Cambridge, England) 59 (2023) 7831–7834; doi:10.1039/d3cc01438j

data_7131723
_publ_section_title
;
 Enantioselective synthesis of 3a-azido-pyrroloindolines by
 copper-catalyzed asymmetric dearomative azidation of tryptamines.
;
_journal_issue                   50
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7831
_journal_page_last               7834
_journal_paper_doi               10.1039/d3cc01438j
_journal_volume                  59
_journal_year                    2023
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C18 H16 N5 O'
_chemical_formula_sum            'C18 H16 N5 O'
_chemical_formula_weight         318.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-16 deposited with the CCDC.	2023-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.9211(2)
_cell_length_b                   8.4929(2)
_cell_length_c                   24.4236(7)
_cell_measurement_reflns_used    9278
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.079
_cell_measurement_theta_min      5.870
_cell_volume                     1643.05(7)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      293.42
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0802
_diffrn_reflns_av_unetI/netI     0.0545
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            14493
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.106
_diffrn_reflns_theta_min         5.872
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.681
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5984
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1480 before and 0.0624 after correction. The Ratio of minimum to maximum transmission is 0.7944. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       prism
_exptl_crystal_F_000             668
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.275
_refine_diff_density_min         -0.158
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 918 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         3087
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0465
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0661P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1108
_refine_ls_wR_factor_ref         0.1139
_reflns_Friedel_coverage         0.718
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                2628
_reflns_number_total             3087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc01438j2.cif
_cod_data_source_block           cu_210604lcz_0m
_cod_depositor_comments          'Adding full bibliography for 7131723.cif.'
_cod_database_code               7131723
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.948
_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:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              63927
_shelx_hkl_checksum              54620
_olex2_submission_special_instructions 'No special instructions were received'