Aromatic C-H Bond Functionalized via Zwitterion Intermediates to Construct Bioxindole Containing Continuous Quaternary Carbons.
Niu, Li; Pi, Rou; Dong, Suzhen; Liu, Shunying; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b02228

data_4036065
_publ_section_title
;
 Aromatic C-H Bond Functionalized via Zwitterion Intermediates to
 Construct Bioxindole Containing Continuous Quaternary Carbons.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02228
_journal_year                    2019
_chemical_formula_moiety         'C55 H49 Cl N4 O4'
_chemical_formula_sum            'C55 H49 Cl N4 O4'
_chemical_formula_weight         865.43
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                65.3620(10)
_cell_angle_beta                 78.6210(10)
_cell_angle_gamma                61.0720(10)
_cell_formula_units_Z            2
_cell_length_a                   13.76020(10)
_cell_length_b                   13.8078(2)
_cell_length_c                   16.1032(2)
_cell_measurement_reflns_used    30898
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.1860
_cell_measurement_theta_min      4.0230
_cell_volume                     2434.00(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.972
_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    -21.00  33.00   0.50    1.00    --    0.00  57.00 120.00  108
  2  \w    -19.00  86.00   0.50    1.00    --    0.00  57.00   0.00  210
  3  \w    -19.00  46.00   0.50    1.00    --    0.00  38.00 -30.00  130
  4  \w    -19.00  28.00   0.50    1.00    --    0.00  38.00-120.00   94
  5  \w     26.00  85.00   0.50    1.00    --    0.00  82.00 150.00  118
  6  \w     40.00  78.00   0.50    1.00    --    0.00  38.00-120.00   76
  7  \w     36.00  81.00   0.50    1.00    --    0.00  38.00  60.00   90
  8  \w     52.00  89.00   0.50    1.00    --    0.00  38.00 -30.00   74
  9  \w    -31.00  22.00   0.50    1.00    --    0.00  82.00 150.00  106
 10  \w     46.00  73.00   0.50    1.00    --    0.00  57.00 120.00   54
 11  \w    -18.00  25.00   0.50    1.00    --    0.00  38.00  60.00   86
 12  \w     54.00  87.00   0.50    1.00    --    0.00  57.00-120.00   66
 13  \w     -6.00  19.00   0.50    1.00    --    0.00  57.00-120.00   50
 14  \w    157.00 183.00   0.50    1.00    --   95.80  70.00  34.35   52
 15  \w     68.00  94.00   0.50    1.00    --   95.80  70.00  34.35   52
 16  \w     97.00 185.00   0.50    1.00    --   95.80  80.00 -74.10  176
 17  \w     68.00  93.00   0.50    1.00    --   95.80  70.00 -62.85   50
 18  \w     69.00  95.00   0.50    1.00    --   95.80  65.00 100.83   52
 19  \w     64.00  90.00   0.50    1.00    --   95.80  80.00 -74.10   52
 20  \w     69.00  94.00   0.50    1.00    --   95.80  67.00-112.48   50
 21  \w     71.00  97.00   0.50    1.00    --   95.80  61.00  60.00   52
 22  \w     65.00  90.00   0.50    1.00    --   95.80  77.00 150.00   50
 23  \w     71.00  98.00   0.50    1.00    --   95.80  61.00 150.00   54
 24  \w     63.00  88.00   0.50    1.00    --   95.80  82.00   0.00   50
 25  \w     93.00 184.00   0.50    1.00    --   95.80  82.00   0.00  182
 26  \w     43.00 126.00   0.50    1.00    --   95.80 -82.00  60.00  166
 27  \w      7.00 126.00   0.50    1.00    --   95.80 -77.00 -90.00  238
 28  \w     63.00  89.00   0.50    1.00    --   95.80  82.00 -60.00   52
 29  \w    129.00 185.00   0.50    1.00    --   95.80  82.00 -60.00  112
 30  \w     65.00  96.00   0.50    1.00    --   95.80  77.00-150.00   62
 31  \w     71.00 184.00   0.50    1.00    --   95.80  59.00  98.58  226
 32  \w     55.00 126.00   0.50    1.00    --   95.80 -82.00-150.00  142
 33  \w     21.00  50.00   0.50    1.00    --   95.80 -82.00-150.00   58
 34  \w    136.00 162.00   0.50    1.00    --   95.80  82.00 -18.00   52
 35  \w     70.00 107.00   0.50    1.00    --   95.80  64.00 127.23   74
 36  \w     63.00 146.00   0.50    1.00    --   95.80  82.00-180.00  166
 37  \w    142.00 183.00   0.50    1.00    --   95.80  61.00-180.00   82
 38  \w     71.00 103.00   0.50    1.00    --   95.80  61.00-180.00   64
 39  \w     35.00  75.00   0.50    1.00    --   95.80 -82.00 120.00   80
 40  \w     89.00 127.00   0.50    1.00    --   95.80 -82.00 120.00   76
 41  \w     65.00  91.00   0.50    1.00    --   95.80  77.00 -30.00   52
 42  \w     46.00  71.00   0.50    1.00    --   95.80 -82.00 -30.00   50
 43  \w     85.00 126.00   0.50    1.00    --   95.80 -82.00 -30.00   82
 44  \w     63.00  88.00   0.50    1.00    --   95.80  82.00-150.00   50
 45  \w     63.00 111.00   0.50    1.00    --   95.80  82.00 -18.00   96
 46  \w     63.00  88.00   0.50    1.00    --   95.80  82.00  60.00   50
 47  \w     75.00 176.00   0.50    1.00    --   95.80  45.00 -90.00  202
 48  \w    118.00 183.00   0.50    1.00    --   95.80  61.00 150.00  130
 49  \w     63.00  89.00   0.50    1.00    --   95.80  82.00-120.00   52
 50  \w     63.00  88.00   0.50    1.00    --   95.80  82.00  90.00   50
 51  \w     63.00  88.00   0.50    1.00    --   95.80  82.00 -30.00   50
 52  \w    115.00 185.00   0.50    1.00    --   95.80  82.00 120.00  140
 53  \w    149.00 176.00   0.50    1.00    --   95.80  73.00 175.72   54
 54  \w     75.00 106.00   0.50    1.00    --   95.80  45.00 -60.00   62
 55  \w     65.00  91.00   0.50    1.00    --   95.80  77.00-120.00   52
 56  \w     77.00 103.00   0.50    1.00    --   95.80  45.00-180.00   52
 57  \w    123.00 149.00   0.50    1.00    --   95.80  45.00-180.00   52
 58  \w     75.00 109.00   0.50    1.00    --   95.80  45.00  60.00   68
 59  \w    116.00 185.00   0.50    1.00    --   95.80  45.00  60.00  138
 60  \w     66.00  92.00   0.50    1.00    --   95.80  77.00  30.00   52
 61  \w     65.00  91.00   0.50    1.00    --   95.80  77.00  60.00   52
 62  \w     75.00 179.00   0.50    1.00    --   95.80  45.00   0.00  208
 63  \w     65.00  91.00   0.50    1.00    --   95.80  77.00 120.00   52
 64  \w     65.00  90.00   0.50    1.00    --   95.80  77.00 -90.00   50
 65  \w     63.00  88.00   0.50    1.00    --   95.80  82.00 120.00   50
 66  \w     72.00  98.00   0.50    1.00    --   95.80  61.00  30.00   52
 67  \w     71.00 104.00   0.50    1.00    --   95.80  61.00 -60.00   66
 68  \w    145.00 183.00   0.50    1.00    --   95.80  77.00-150.00   76
 69  \w     67.00  92.00   0.50    1.00    --   95.80  73.00 175.72   50
 70  \w     66.00 117.00   0.50    1.00    --   95.80  77.00 -60.00  102
 71  \w     74.00 176.00   0.50    1.00    --   95.80  51.00  83.71  204
 72  \w    152.00 178.00   0.50    1.00    --   95.80  67.00-112.48   52
 73  \w     72.00  98.00   0.50    1.00    --   95.80  61.00 120.00   52
 74  \w    126.00 181.00   0.50    1.00    --   95.80  33.00-119.53  110
 75  \w     78.00 123.00   0.50    1.00    --   95.80  33.00-119.53   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1187127000
_diffrn_orient_matrix_UB_12      0.0495553000
_diffrn_orient_matrix_UB_13      -0.0327952000
_diffrn_orient_matrix_UB_21      0.0420949000
_diffrn_orient_matrix_UB_22      0.0188174000
_diffrn_orient_matrix_UB_23      -0.0988400000
_diffrn_orient_matrix_UB_31      0.0223291000
_diffrn_orient_matrix_UB_32      -0.1268610000
_diffrn_orient_matrix_UB_33      0.0152620000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            62386
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.654
_diffrn_reflns_theta_min         3.945
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.078
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71067
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.181
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.546
_refine_diff_density_min         -0.496
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       0.0015(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         9714
_refine_ls_number_restraints     89
_refine_ls_restrained_S_all      1.255
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0488
_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^)+(0.0845P)^2^+0.4597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1471
_refine_ls_wR_factor_ref         0.1504
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8641
_reflns_number_total             9714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02228_si_002.cif
_cod_data_source_block           exp_670
_cod_database_code               4036065
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.724
_shelx_estimated_absorpt_t_min   0.637
_reflns_odcompleteness_completeness 99.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Rigid bond restraints
 C30, C29, C28, C27, C26, C25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C50, C49
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C49, C48, C47
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C45, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C28 \\sim C29 \\sim C30 \\sim C27 \\sim C26 \\sim C25: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.08
C49 \\sim C50: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C49 \\sim C48 \\sim C47: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C45 \\sim C50: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C49) \\sim Ueq, Uanis(C50) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C24(H24A,H24B), C37(H37A,H37B), C44(H44A,H44B)
4.b Aromatic/amide H refined with riding coordinates:
 N3(H3), C1(H1), C2(H2), C3(H3A), C4(H4), C5(H5), C12(H12), C13(H13), C15(H15),
  C19(H19), C20(H20), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28),
 C29(H29), C30(H30), C32(H32), C33(H33), C35(H35), C36(H36), C39(H39), C40(H40),
  C41(H41), C42(H42), C43(H43), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50)
4.c Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C)
;
_shelx_res_checksum              65263
_shelx_hkl_checksum              22518
_shelx_fab_checksum              93946
_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 1.291
_oxdiff_exptl_absorpt_empirical_full_min 0.594