Synthesis of 4-Azaindolines Using Phase-Transfer Catalysis via an Intramolecular Mannich Reaction.
Wang, Jingdong; Liu, Yuxin; Wei, Zhonglin; Cao, Jungang; Liang, Dapeng; Lin, Yingjie; Duan, Haifeng; The Journal of organic chemistry 85 (2020) 4047–4057; doi:10.1021/acs.joc.9b03025

data_4038052
_publ_section_title
;
 Synthesis of 4-Azaindolines Using Phase-Transfer Catalysis via an
 Intramolecular Mannich Reaction.
;
_journal_issue                   6
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4047
_journal_page_last               4057
_journal_paper_doi               10.1021/acs.joc.9b03025
_journal_volume                  85
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H15 Cl N3'
_chemical_formula_sum            'C20 H15 Cl N3'
_chemical_formula_weight         1996.80
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-10-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.325(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            6
_cell_length_a                   9.2518(9)
_cell_length_b                   13.2729(13)
_cell_length_c                   20.695(2)
_cell_measurement_reflns_used    2804
_cell_measurement_temperature    273
_cell_measurement_theta_max      22.811
_cell_measurement_theta_min      2.201
_cell_volume                     2541.3(4)
_computing_cell_refinement       'SAINT v6.45A (Bruker, 2003)'
_computing_data_reduction        'SAINT v6.45A (Bruker, 2003)'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      273
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'CCD Area Detector'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0355
_diffrn_reflns_av_unetI/netI     0.0696
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            14507
_diffrn_reflns_theta_full        26.38
_diffrn_reflns_theta_max         26.38
_diffrn_reflns_theta_min         1.82
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.230
_exptl_absorpt_correction_T_max  0.9998
_exptl_absorpt_correction_T_min  0.706579
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS v.2.10 (Bruker,2003) was used for absorption correction.
R(int) was 0.0801 before and 0.0288 after correction.
The Ratio of minimum to maximum transmission is 0.7066.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1038
_exptl_crystal_size_max          0.001
_exptl_crystal_size_mid          0.001
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.709
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.07(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     649
_refine_ls_number_reflns         8697
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0966
_refine_ls_R_factor_gt           0.0591
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0731P)^2^+0.1907P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1325
_refine_ls_wR_factor_ref         0.1538
_reflns_number_gt                5893
_reflns_number_total             8697
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9b03025_si_001.cif
_cod_data_source_block           ca184m
_cod_depositor_comments
;
         Adding full bibliography for 4038052.cif.

2020-11-04
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C120 H90 Cl6 N18'
_cod_original_formula_weight         1996.80
_cod_original_formula_moiety         '6(C20 H15 Cl N3)'
_cod_original_formula_units_Z            1
_cod_database_code               4038052
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. Rigid bond restraints
 N39, C59
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C54, C67
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N2, C3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C6, N18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N18, C38
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3.a Ternary CH refined with riding coordinates:
 C9(H9), C20(H20), C35(H35)
3.b Aromatic/amide H refined with riding coordinates:
 N2(H2), N7(H7), C11(H11), N14(H14), C15(H15), C17(H17), N18(H18), C19(H19),
 C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C29(H29), C30(H30), C31(H31),
  C33(H33), C34(H34), C36(H36), C37(H37), C38(H38), N39(H39), C40(H40),
 C41(H41), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48), C50(H50), C51(H51),
  C52(H52), C54(H54), C55(H55), C56(H56), C58(H58), C62(H62), C63(H63),
 C66(H66), C67(H67), N68(H68), C70(H70)
;
_olex2_submission_special_instructions 'No special instructions were received'