Organocatalytic intramolecular (4 + 2) annulation of enals with ynamides: atroposelective synthesis of axially chiral 7-aryl indolines.
Zhang, Zhi-Xin; Liu, Li-Gao; Liu, Yi-Xi; Lin, Jian; Lu, Xin; Ye, Long-Wu; Zhou, Bo; Chemical science 14 (2023) 5918–5924; doi:10.1039/d3sc01880f

data_1569055
_publ_section_title
;
 Organocatalytic intramolecular (4 + 2) annulation of enals with ynamides:
 atroposelective synthesis of axially chiral 7-aryl indolines.
;
_journal_issue                   22
_journal_name_full               'Chemical science'
_journal_page_first              5918
_journal_page_last               5924
_journal_paper_doi               10.1039/d3sc01880f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C26 H20 F3 N O5 S2'
_chemical_formula_sum            'C26 H20 F3 N O5 S2'
_chemical_formula_weight         547.55
_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     dual
_audit_creation_date             2021-11-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-01-06 deposited with the CCDC.	2023-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.455(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.99780(10)
_cell_length_b                   14.4109(3)
_cell_length_c                   12.2598(2)
_cell_measurement_reflns_used    18576
_cell_measurement_temperature    99.9(7)
_cell_measurement_theta_max      75.1490
_cell_measurement_theta_min      3.6310
_cell_volume                     1235.94(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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_environment      N~2~
_diffrn_ambient_temperature      99.9(7)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.958
_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     76.00 119.00   0.50    0.15    --  109.59  18.00 -24.00   86
  2  \w    127.00 154.00   0.50    0.15    --  109.59  18.00 -24.00   54
  3  \w     84.00 119.00   0.50    0.05    --   43.09  18.00 -24.00   70
  4  \w     52.00  82.00   0.50    0.05    --   43.09  18.00 -24.00   60
  5  \w     22.00  84.00   0.50    0.05    --   43.09  57.00  30.00  124
  6  \w    -86.00 -42.00   0.50    0.05    --  -43.09 -18.00 167.00   88
  7  \w   -117.00 -71.00   0.50    0.05    --  -43.09 -77.00  90.00   92
  8  \w    -65.00 -14.00   0.50    0.05    --  -43.09 -77.00  90.00  102
  9  \w    -87.00 -17.00   0.50    0.05    --  -43.09 -64.00 142.03  140
 10  \w    -69.00 -14.00   0.50    0.05    --  -43.09 -77.00  30.00  110
 11  \w   -118.00 -74.00   0.50    0.05    --  -43.09 -77.00  30.00   88
 12  \w    -73.00 -12.00   0.50    0.05    --  -43.09 -77.00 -60.00  122
 13  \w    -79.00 -12.00   0.50    0.05    --  -43.09 -77.00-150.00  134
 14  \w    -95.00 -57.00   0.50    0.05    --  -43.09 -57.00-120.00   76
 15  \w    -56.00 -19.00   0.50    0.05    --  -43.09 -57.00-120.00   74
 16  \w   -120.00 -87.00   0.50    0.05    --  -43.09 -18.00 167.00   66
 17  \w    -76.00 -19.00   0.50    0.05    --  -43.09 -37.00  90.00  114
 18  \w     -9.00  37.00   0.50    0.05    --  -43.09  18.00 -24.00   92
 19  \w   -100.00 -31.00   0.50    0.15    --  -96.00  77.00 -60.00  138
 20  \w   -101.00 -32.00   0.50    0.15    --  -96.00  77.00-120.00  138
 21  \w   -103.00 -46.00   0.50    0.15    --  -96.00  77.00  90.00  114
 22  \w    -89.00 -50.00   0.50    0.15    --  -96.00 125.00 120.00   78
 23  \w      5.00  31.00   0.50    0.05    --   43.09  95.00 -10.69   52
 24  \w      4.00  29.00   0.50    0.05    --   43.09  95.00 157.47   50
 25  \w     61.00 124.00   0.50    0.05    --   43.09 178.00-150.00  126
 26  \w    -38.00   0.00   0.50    0.05    --   43.09 -18.00 167.00   76
 27  \w     38.00  80.00   0.50    0.15    --  109.59-125.00 120.00   84
 28  \w     84.00 114.00   0.50    0.15    --  109.59-125.00 120.00   60
 29  \w     62.00 115.00   0.50    0.15    --  109.59-125.00 150.00  106
 30  \w     57.00 119.00   0.50    0.05    --   43.09-178.00  60.00  124
 31  \w     64.00 111.00   0.50    0.15    --  109.59-125.00  30.00   94
 32  \w     60.00 108.00   0.50    0.15    --  109.59-125.00   0.00   96
 33  \w     43.00  88.00   0.50    0.15    --  109.59 -94.00  30.00   90
 34  \w     72.00 116.00   0.50    0.15    --  109.59-125.00 -60.00   88
 35  \w     81.00 116.00   0.50    0.15    --  109.59-125.00-120.00   70
 36  \w     46.00  77.00   0.50    0.15    --  109.59-125.00-120.00   62
 37  \w   -168.00-141.00   0.50    0.15    --  -96.00 -81.00 -34.74   54
 38  \w   -146.00-119.00   0.50    0.15    --  -96.00 -83.00 109.17   54
 39  \w    -94.00 -62.00   0.50    0.15    --  -96.00 -83.00 109.17   64
 40  \w    -88.00 -63.00   0.50    0.15    --  -96.00 -82.00 152.76   50
 41  \w    -89.00 -62.00   0.50    0.15    --  -96.00 -83.00 -43.92   54
 42  \w   -103.00 -63.00   0.50    0.15    --  -96.00 -82.00-103.18   80
 43  \w   -160.00-112.00   0.50    0.15    --  -96.00 -82.00-103.18   96
 44  \w   -168.00-116.00   0.50    0.15    --  -96.00 -82.00-178.36  104
 45  \w    -90.00 -63.00   0.50    0.15    --  -96.00 -82.00-178.36   54
 46  \w   -118.00 -62.00   0.50    0.05    --  -43.09-178.00-180.00  112
 47  \w    -90.00 -63.00   0.50    0.15    --  -96.00 -81.00 -34.74   54
 48  \w    -98.00 -65.00   0.50    0.15    --  -96.00 -77.00  60.00   66
 49  \w   -170.00 -65.00   0.50    0.15    --  -96.00 -77.00 120.00  210
 50  \w   -170.00 -65.00   0.50    0.15    --  -96.00 -77.00 -13.67  210
 51  \w    -91.00 -65.00   0.50    0.15    --  -96.00 -77.00 -90.00   52
 52  \w   -113.00 -65.00   0.50    0.15    --  -96.00 -77.00-120.00   96
 53  \w   -131.00 -65.00   0.50    0.15    --  -96.00 -77.00-150.00  132
 54  \w   -169.00-137.00   0.50    0.15    --  -96.00 -77.00-150.00   64
 55  \w   -153.00-115.00   0.50    0.15    --  -96.00 -77.00-120.00   76
 56  \w   -153.00-119.00   0.50    0.15    --  -96.00 -77.00 -30.00   68
 57  \w   -168.00-124.00   0.50    0.15    --  -96.00 -77.00   0.00   88
 58  \w   -169.00 -67.00   0.50    0.15    --  -96.00 -75.00  74.60  204
 59  \w    -92.00 -66.00   0.50    0.15    --  -96.00 -74.00  62.68   52
 60  \w    -90.00 -65.00   0.50    0.15    --  -96.00 -77.00   0.00   50
 61  \w   -101.00 -66.00   0.50    0.15    --  -96.00 -74.00  39.68   70
 62  \w    -91.00 -66.00   0.50    0.15    --  -96.00 -74.00  32.99   50
 63  \w   -167.00 -94.00   0.50    0.15    --  -96.00 -74.00  32.99  146
 64  \w   -165.00-102.00   0.50    0.15    --  -96.00 -74.00  39.68  126
 65  \w    -93.00 -67.00   0.50    0.15    --  -96.00 -73.00  78.50   52
 66  \w   -165.00 -71.00   0.50    0.15    --  -96.00 -73.00 136.01  188
 67  \w   -163.00-117.00   0.50    0.15    --  -96.00 -73.00  78.50   92
 68  \w   -109.00 -65.00   0.50    0.15    --  -96.00 -77.00 -30.00   88
 69  \w    -97.00 -67.00   0.50    0.15    --  -96.00 -71.00  43.11   60
 70  \w   -166.00 -67.00   0.50    0.15    --  -96.00 -72.00 -87.84  198
 71  \w   -168.00 -66.00   0.50    0.15    --  -96.00 -74.00-167.59  204
 72  \w   -170.00 -65.00   0.50    0.15    --  -96.00 -76.00-134.72  210
 73  \w   -151.00 -68.00   0.50    0.15    --  -96.00 -70.00 -70.47  166
 74  \w   -166.00-141.00   0.50    0.15    --  -96.00 -65.00  -4.94   50
 75  \w   -113.00 -70.00   0.50    0.15    --  -96.00 -65.00  -4.94   86
 76  \w    -97.00 -70.00   0.50    0.15    --  -96.00 -61.00   0.00   54
 77  \w   -128.00 -68.00   0.50    0.15    --  -96.00 -69.00 145.30  120
 78  \w   -169.00-131.00   0.50    0.15    --  -96.00 -69.00 145.30   76
 79  \w   -139.00-112.00   0.50    0.15    --  -96.00 -18.00 167.00   54
;
_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      0.1865414000
_diffrn_orient_matrix_UB_12      0.0082431000
_diffrn_orient_matrix_UB_13      0.0688299000
_diffrn_orient_matrix_UB_21      0.1099724000
_diffrn_orient_matrix_UB_22      0.0241189000
_diffrn_orient_matrix_UB_23      -0.1035048000
_diffrn_orient_matrix_UB_31      -0.0404905000
_diffrn_orient_matrix_UB_32      0.1037911000
_diffrn_orient_matrix_UB_33      0.0186231000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0856
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            27281
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.214
_diffrn_reflns_theta_min         3.606
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.505
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.18102
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
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    1.471
_exptl_crystal_description       block
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.491
_refine_diff_density_min         -0.442
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 1984 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.023(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         4648
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0478
_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^)+(0.1000P)^2^+0.1740P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1294
_refine_ls_wR_factor_ref         0.1351
_reflns_Friedel_coverage         0.832
_reflns_Friedel_fraction_full    0.949
_reflns_Friedel_fraction_max     0.865
_reflns_number_gt                4522
_reflns_number_total             4648
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01880f2.cif
_cod_data_source_block           exp_7542_auto
_cod_depositor_comments          'Adding full bibliography for 1569055.cif.'
_cod_database_code               1569055
_shelxl_version_number           2013-2
_diffrn_oxdiff_digest_frames
;
0171553add485a4790c7d0421f1d423ff9000864508
;
_diffrn_oxdiff_digest_hkl
;
01c50f27440447bd16e984c13a7679d175d25a
;
_reflns_odcompleteness_completeness 100.00
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C12(H12), C13(H13), C14(H14),
 C21(H21), C23(H23), C24(H24), C26(H26)
2.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_shelx_res_checksum              63765
_shelx_hkl_checksum              40194
_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 4.085
_oxdiff_exptl_absorpt_empirical_full_min 0.344