Nitrogen-interrupted <i>halo</i>-Prins/<i>halo</i>-Nazarov fragment coupling cascade for the synthesis of indolines.
Milosavljevic, Aleksa; Holt, Connor; Frontier, Alison J.; Chemical science 14 (2023) 5431–5437; doi:10.1039/d3sc00986f

data_1568949
_publ_section_title
;
 Nitrogen-interrupted <i>halo</i>-Prins/<i>halo</i>-Nazarov fragment
 coupling cascade for the synthesis of indolines.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              5431
_journal_page_last               5437
_journal_paper_doi               10.1039/d3sc00986f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C27 H32 I N O3 S'
_chemical_formula_sum            'C27 H32 I N O3 S'
_chemical_formula_weight         577.49
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-01-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-07 deposited with the CCDC.	2023-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                82.958(2)
_cell_angle_beta                 72.346(2)
_cell_angle_gamma                62.821(3)
_cell_formula_units_Z            2
_cell_length_a                   10.0403(3)
_cell_length_b                   10.7542(3)
_cell_length_c                   13.6818(2)
_cell_measurement_reflns_used    30966
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      80.0210
_cell_measurement_theta_min      3.3910
_cell_volume                     1252.07(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.981
_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    -14.00  28.00   0.50    0.05    --  -47.28  19.00 150.00   84
  2  \w    -14.00  28.00   0.50    0.05    --  -47.28  19.00 120.00   84
  3  \w    -14.00  28.00   0.50    0.05    --  -47.28  19.00   0.00   84
  4  \w    -14.00  28.00   0.50    0.05    --  -47.28  19.00 -30.00   84
  5  \w    -14.00  28.00   0.50    0.05    --  -47.28  19.00-120.00   84
  6  \w    -14.00  28.00   0.50    0.05    --  -47.28  19.00-150.00   84
  7  \w     25.00 120.00   0.50    0.05    --   47.28  77.00 -60.00  190
  8  \w     35.00 120.00   0.50    0.05    --   47.28  38.00 -60.00  170
  9  \w     97.00 178.00   0.50    0.10    --  113.25  61.00  30.00  162
 10  \w     25.00 120.00   0.50    0.05    --   47.28  77.00  30.00  190
 11  \w     91.00 178.00   0.50    0.10    --  113.25  77.00 -60.00  174
 12  \w     97.00 178.00   0.50    0.10    --  113.25  61.00 -90.00  162
 13  \w    101.00 178.00   0.50    0.10    --  113.25  45.00-150.00  154
 14  \w    101.00 178.00   0.50    0.10    --  113.25  30.00-180.00  154
 15  \w    101.00 178.00   0.50    0.10    --  113.25  30.00 -30.00  154
 16  \w    101.00 178.00   0.50    0.10    --  113.25  30.00  30.00  154
 17  \w    101.00 178.00   0.50    0.10    --  113.25  30.00  60.00  154
 18  \w    101.00 178.00   0.50    0.10    --  113.25  30.00  90.00  154
 19  \w    100.00 178.00   0.50    0.10    --  113.25  15.00 150.00  156
 20  \w     86.00 174.00   0.50    0.10    --  113.25 139.00  27.00  176
 21  \w     91.00 178.00   0.50    0.10    --  113.25 131.00-147.00  174
 22  \w     42.00  76.00   0.50    0.10    --  113.25 -61.00-180.00   68
 23  \w     42.00  76.00   0.50    0.10    --  113.25 -61.00-150.00   68
 24  \w     42.00  76.00   0.50    0.10    --  113.25 -61.00 -60.00   68
 25  \w     42.00  76.00   0.50    0.10    --  113.25 -61.00   0.00   68
 26  \w     42.00  76.00   0.50    0.10    --  113.25 -61.00  90.00   68
 27  \w     42.00  76.00   0.50    0.10    --  113.25 -61.00 120.00   68
 28  \w     42.00  76.00   0.50    0.10    --  113.25 -61.00 150.00   68
 29  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00 120.00  128
 30  \w     43.00 116.00   0.50    0.10    --  113.25-131.00 141.00  146
 31  \w     38.00  97.00   0.50    0.05    --   47.28-131.00 141.00  118
 32  \w     42.00 122.00   0.50    0.10    --  113.25-139.00 -33.00  160
 33  \w     47.00 129.00   0.50    0.10    --  113.25-149.00 -35.44  164
 34  \w     44.00 111.00   0.50    0.10    --  113.25-125.00 -90.00  134
 35  \w     44.00 111.00   0.50    0.10    --  113.25-125.00-120.00  134
 36  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00 -60.00  128
 37  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00 -30.00  128
 38  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00   0.00  128
 39  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00  30.00  128
 40  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00  60.00  128
 41  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00  90.00  128
 42  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00 150.00  128
 43  \w     42.00 103.00   0.50    0.05    --   47.28-139.00 -33.00  122
 44  \w     42.00 106.00   0.50    0.10    --  113.25 -94.00 -90.00  128
 45  \w    -96.00 -20.00   0.50    0.05    --  -47.28 139.00  27.00  152
 46  \w    -91.00 -21.00   0.50    0.10    --  -91.75 131.00-147.00  140
 47  \w    -90.00 -16.00   0.50    0.05    --  -47.28 131.00-147.00  148
 48  \w   -163.00 -95.00   0.50    0.10    --  -91.75 -77.00 150.00  136
 49  \w   -163.00 -69.00   0.50    0.10    --  -91.75 -77.00 120.00  188
 50  \w   -163.00 -69.00   0.50    0.10    --  -91.75 -77.00  45.09  188
 51  \w   -163.00 -69.00   0.50    0.10    --  -91.75 -76.00  -5.33  188
 52  \w   -163.00 -71.00   0.50    0.10    --  -91.75 -73.00 -86.79  184
 53  \w   -163.00 -71.00   0.50    0.10    --  -91.75 -72.00-135.99  184
 54  \w   -163.00 -69.00   0.50    0.10    --  -91.75 -77.00-180.00  188
 55  \w   -166.00 -78.00   0.50    0.10    --  -91.75 -15.00-180.00  176
 56  \w   -163.00 -75.00   0.50    0.10    --  -91.75 -61.00 -60.00  176
 57  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00 120.00  188
 58  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00 150.00  188
 59  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00  90.00  188
 60  \w   -119.00 -32.00   0.50    0.05    --  -47.28 -57.00 150.00  174
 61  \w   -119.00 -32.00   0.50    0.05    --  -47.28 -57.00   0.00  174
 62  \w   -119.00 -29.00   0.50    0.05    --  -47.28 -65.00 -45.61  180
 63  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00 -90.00  188
 64  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00-150.00  188
 65  \w   -119.00 -64.00   0.50    0.05    --  -47.28-139.00 -33.00  110
 66  \w   -157.00 -64.00   0.50    0.10    --  -91.75-139.00 -33.00  186
 67  \w   -118.00 -70.00   0.50    0.05    --  -47.28-131.00 141.00   96
 68  \w   -162.00 -70.00   0.50    0.10    --  -91.75-131.00 141.00  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0418507000
_diffrn_orient_matrix_UB_12      0.0045841000
_diffrn_orient_matrix_UB_13      -0.1179984000
_diffrn_orient_matrix_UB_21      -0.0845166000
_diffrn_orient_matrix_UB_22      0.1609530000
_diffrn_orient_matrix_UB_23      0.0056633000
_diffrn_orient_matrix_UB_31      0.1529311000
_diffrn_orient_matrix_UB_32      0.0037395000
_diffrn_orient_matrix_UB_33      -0.0034665000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0479
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            42710
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.461
_diffrn_reflns_theta_min         3.391
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.054
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36742
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (Rigaku Oxford Diffraction, 2023)
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    1.532
_exptl_crystal_description       plate
_exptl_crystal_F_000             588
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.451
_refine_diff_density_min         -0.920
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         5389
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0294
_refine_ls_R_factor_gt           0.0288
_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^)+(0.0291P)^2^+1.9228P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0727
_refine_ls_wR_factor_ref         0.0732
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5251
_reflns_number_total             5389
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00986f2.cif
_cod_data_source_block           froam06
_cod_depositor_comments
'Adding full bibliography for 1568947--1568949.cif.'
_cod_original_cell_volume        1252.07(6)
_cod_database_code               1568949
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.597
_shelx_estimated_absorpt_t_min   0.216
_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, All O(H) groups
2. Restrained distances
 C1-C17 \\sim C1-C17'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.2A
C17 \\sim C17': within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
4. Same fragment restrains
{C17, C18, C19, C20, O1} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C17', C18', C19', C20', O1'}
5. Others
 Sof(C17')=Sof(H17C)=Sof(H17D)=Sof(C18')=Sof(H18C)=Sof(H18D)=Sof(C19')=
 Sof(H19')=Sof(C20')=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(O1')=Sof(H1')=1-FVAR(1)
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(O1)=Sof(H1)=FVAR(1)
6.a Riding coordinates:
 O1'(H1')
6.b Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C19(H19), C19'(H19')
6.c Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C17(H17A,
 H17B), C18(H18A,H18B), C17'(H17C,H17D), C18'(H18C,H18D)
6.d Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C16(H16), C22(H22), C23(H23), C25(H25), C26(H26)
6.e Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C20'(H20D,H20E,H20F), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              49458
_shelx_hkl_checksum              31375
_olex2_submission_original_sample_id froam06
_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 2.090
_oxdiff_exptl_absorpt_empirical_full_min 0.720