Diastereoselective synthesis of polycyclic indolines <i>via</i> dearomative [4 + 2] cycloaddition of 3-nitroindoles with <i>ortho</i>-aminophenyl <i>p</i>-quinone methides.
Zhou, Shun; Qian, Hui-Ling; Zhao, Jian-Qiang; You, Yong; Wang, Zhen-Hua; Yin, Jun-Qing; Zhang, Yan-Ping; Chen, Ming-Feng; Yuan, Wei-Cheng; Organic & biomolecular chemistry 21 (2023) 1373–1378; doi:10.1039/d2ob02303b

data_7159098
_publ_section_title
;
 Diastereoselective synthesis of polycyclic indolines <i>via</i>
 dearomative [4 + 2] cycloaddition of 3-nitroindoles with
 <i>ortho</i>-aminophenyl <i>p</i>-quinone methides.
;
_journal_issue                   7
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1373
_journal_page_last               1378
_journal_paper_doi               10.1039/d2ob02303b
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C43 H45 N3 O7 S2'
_chemical_formula_sum            'C43 H45 N3 O7 S2'
_chemical_formula_weight         779.94
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-07-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-11-02 deposited with the CCDC.	2023-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.9954(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.5995(2)
_cell_length_b                   10.0324(2)
_cell_length_c                   27.7318(5)
_cell_measurement_reflns_used    6229
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7670
_cell_measurement_theta_min      4.7040
_cell_volume                     3923.50(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.978
_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    -82.00 -20.00   1.00    2.00    --  -33.50 -57.00  90.00   62
  2  \w   -106.00 -80.00   1.00    2.00    --  -33.50 178.00   0.00   26
  3  \w    -65.00 -39.00   1.00    2.00    --  -33.50 178.00 -90.00   26
  4  \w   -107.00 -78.00   1.00    2.00    --  -33.50 178.00 -90.00   29
  5  \w     48.00  73.00   1.00    2.00    --   36.47 -99.00-120.00   25
  6  \w     39.00  66.00   1.00    2.00    --   36.47 -99.00 -30.00   27
  7  \w     39.00  76.00   1.00    2.00    --   36.47 -99.00 120.00   37
  8  \w     -2.00  33.00   1.00    2.00    --   36.47 -99.00-120.00   35
  9  \w     27.00  74.00   1.00    2.00    --   36.47 -19.00-120.00   47
 10  \w    -17.00  74.00   1.00    2.00    --   36.47 -19.00  60.00   91
 11  \w     79.00 105.00   1.00    2.00    --   36.47 178.00  30.00   26
 12  \w      0.00  25.00   1.00    2.00    --   36.47 -99.00 -30.00   25
 13  \w     -4.00  27.00   1.00    2.00    --   36.47 -99.00 120.00   31
 14  \w     57.00  82.00   1.00    2.00    --   36.47 178.00-150.00   25
 15  \w    -35.00   1.00   1.00    2.00    --   36.47 -19.00-120.00   36
 16  \w    110.00 173.00   1.00    7.50    --  108.00  30.00  60.00   63
 17  \w     64.00 126.00   1.00    7.50    --  108.00 -61.00  60.00   62
 18  \w    110.00 173.00   1.00    7.50    --  108.00 111.00-150.00   63
 19  \w    133.00 175.00   1.00    7.50    --  108.00  61.00  90.00   42
 20  \w     85.00 111.00   1.00    7.50    --  108.00-111.00 -30.00   26
 21  \w     74.00 108.00   1.00    7.50    --  108.00 -94.00-120.00   34
 22  \w     38.00 109.00   1.00    7.50    --  108.00 -94.00   0.00   71
 23  \w    152.00 178.00   1.00    7.50    --  108.00  45.00 -60.00   26
 24  \w     88.00 116.00   1.00    7.50    --  108.00  45.00 -60.00   28
 25  \w     41.00  67.00   1.00    7.50    --  108.00 -94.00-120.00   26
 26  \w    118.00 176.00   1.00    7.50    --  108.00 111.00  60.00   58
 27  \w     81.00 151.00   1.00    7.50    --  108.00  77.00-180.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0119079000
_diffrn_orient_matrix_UB_12      -0.1525667000
_diffrn_orient_matrix_UB_13      0.0003325000
_diffrn_orient_matrix_UB_21      -0.0171089000
_diffrn_orient_matrix_UB_22      0.0078964000
_diffrn_orient_matrix_UB_23      0.0524520000
_diffrn_orient_matrix_UB_31      -0.1072397000
_diffrn_orient_matrix_UB_32      0.0157317000
_diffrn_orient_matrix_UB_33      -0.0235537000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0350
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            17801
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.051
_diffrn_reflns_theta_min         3.300
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.680
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80232
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             1648
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.705
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         7407
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0552
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0960P)^2^+0.8251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1513
_refine_ls_wR_factor_ref         0.1659
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5817
_reflns_number_total             7407
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob02303b2.cif
_cod_data_source_block           20200722ziq1
_cod_depositor_comments          'Adding full bibliography for 7159098.cif.'
_cod_original_cell_volume        3923.48(13)
_cod_database_code               7159098
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C14H15N2O4S2
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.763
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 N3-O5A
 1.23 with sigma of 0.02
 N3-O5A \\sim N3-O6 \\sim N3-O5 \\sim N3-O6A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O6) = Uanis(O6A)
Uanis(O5) = Uanis(O5A)
4. Others
 Sof(O5A)=Sof(O6A)=1-FVAR(1)
 Sof(O5)=Sof(O6)=FVAR(1)
5.a Riding coordinates:
 O7(H7)
5.b Ternary CH refined with riding coordinates:
 C7(H7A), C9(H9)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C12(H12), C13(H13), C14(H14), C15(H15),
 C17(H17), C21(H21), C31(H31), C32(H32), C34(H34), C35(H35), C38(H38), C39(H39),
  C41(H41), C42(H42)
5.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C), C43(H43A,
 H43B,H43C)
;
_shelx_res_checksum              98805
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.252
_oxdiff_exptl_absorpt_empirical_full_min 0.840