Copper Catalyzed Intramolecular N-Arylation of Ketene Aminals at Room Temperature: Synthesis of 2-Amino-3-cyanoindoles.
Thirupathi, Annaram; Janni, Manojkumar; Peruncheralathan, Saravanan; The Journal of organic chemistry 83 (2018) 8668–8678; doi:10.1021/acs.joc.8b00816

data_4035583
_publ_section_title
;
 Copper Catalyzed Intramolecular N-Arylation of Ketene Aminals at Room
 Temperature: Synthesis of 2-Amino-3-cyanoindoles.
;
_journal_issue                   15
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8668
_journal_page_last               8678
_journal_paper_doi               10.1021/acs.joc.8b00816
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C22 H16 N4 O3'
_chemical_formula_sum            'C22 H16 N4 O3'
_chemical_formula_weight         384.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2018-04-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.799(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4804(7)
_cell_length_b                   12.5579(11)
_cell_length_c                   18.2886(17)
_cell_measurement_reflns_used    1509
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      18.799
_cell_measurement_theta_min      2.936
_cell_volume                     1899.3(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      296.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1435
_diffrn_reflns_av_unetI/netI     0.0874
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            19858
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.669
_diffrn_reflns_theta_min         1.983
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.092
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5089
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1076 before and 0.0696 after correction. The Ratio of minimum to maximum transmission is 0.6829. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       needle
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.249
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.064
_refine_ls_extinction_coef       0.010(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.955
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3531
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.955
_refine_ls_R_factor_all          0.1367
_refine_ls_R_factor_gt           0.0632
_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^)+(0.0908P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1402
_refine_ls_wR_factor_ref         0.1840
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1774
_reflns_number_total             3531
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00816_si_002.cif
_cod_data_source_block           peru_atp-661
_cod_database_code               4035583
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17), C19(H19), C20(H20)
2.c Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C)
;
_shelx_res_checksum              66640
_shelx_hkl_checksum              25848
_olex2_submission_special_instructions 'No special instructions were received'