Visible-light-driven enantioselective intermolecular [2 + 2] photocyclization utilizing bathochromic excitation mediated by a chiral phosphoric acid.
Uchikura, Tatsuhiro; Takahashi, Kazuki; Oishi, Tatsushi; Akiyama, Takahiko; Organic & biomolecular chemistry 21 (2023) 9138–9142; doi:10.1039/d3ob01425h

data_7159661
_publ_section_title
;
 Visible-light-driven enantioselective intermolecular [2 + 2]
 photocyclization utilizing bathochromic excitation mediated by a chiral
 phosphoric acid.
;
_journal_issue                   46
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9138
_journal_page_last               9142
_journal_paper_doi               10.1039/d3ob01425h
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H27 I N2 O2'
_chemical_formula_sum            'C33 H27 I N2 O2'
_chemical_formula_weight         610.46
_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             2021-05-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2023-08-25 deposited with the CCDC.	2023-10-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.158(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0650(2)
_cell_length_b                   25.6508(7)
_cell_length_c                   12.7514(3)
_cell_measurement_reflns_used    45950
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      68.0210
_cell_measurement_theta_min      3.3350
_cell_volume                     2941.90(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_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     96.00 148.00   0.50    0.86    --  114.50  30.00  60.00  104
  2  \w     97.00 177.00   0.50    0.86    --  114.50  45.00 120.00  160
  3  \w    107.00 134.00   0.50    0.86    --  114.50  61.00  90.00   54
  4  \w    136.00 165.00   0.50    0.86    --  114.50  61.00  90.00   58
  5  \w     91.00 164.00   0.50    0.86    --  114.50  30.00 -30.00  146
  6  \w     92.00 176.00   0.50    0.86    --  114.50  30.00-120.00  168
  7  \w      4.00  29.00   0.50    0.21    --  -41.23  19.00-120.00   50
  8  \w    -22.00  39.00   0.50    0.21    --  -41.23  19.00-150.00  122
  9  \w    -22.00  40.00   0.50    0.21    --  -41.23  19.00 -30.00  124
 10  \w    -22.00  36.00   0.50    0.21    --  -41.23  19.00 150.00  116
 11  \w    -99.00 -74.00   0.50    0.86    -- -104.00 137.00 123.00   50
 12  \w    -78.00 -45.00   0.50    0.21    --  -41.23 133.00 -53.00   66
 13  \w    -98.00 -73.00   0.50    0.86    -- -104.00 133.00 -53.00   50
 14  \w     48.00  98.00   0.50    0.21    --   41.23-133.00-122.00  100
 15  \w     87.00 113.00   0.50    0.86    --  114.50-133.00-122.00   52
 16  \w     53.00  80.00   0.50    0.86    --  114.50-133.00-122.00   54
 17  \w     55.00 107.00   0.50    0.86    --  114.50-111.00-120.00  104
 18  \w     48.00 105.00   0.50    0.86    --  114.50-111.00 -90.00  114
 19  \w     41.00 108.00   0.50    0.86    --  114.50-111.00 -60.00  134
 20  \w     42.00  81.00   0.50    0.86    --  114.50-111.00  60.00   78
 21  \w     42.00 120.00   0.50    0.86    --  114.50-137.00  60.00  156
 22  \w     75.00 102.00   0.50    0.86    --  114.50 -95.00 -60.00   54
 23  \w     41.00  81.00   0.50    0.86    --  114.50 -95.00-150.00   80
 24  \w     41.00  68.00   0.50    0.86    --  114.50 -61.00-150.00   54
 25  \w     63.00 107.00   0.50    0.86    --  114.50 -77.00  30.00   88
 26  \w     42.00  73.00   0.50    0.86    --  114.50 -61.00  30.00   62
 27  \w     48.00  73.00   0.50    0.86    --  114.50 -61.00  90.00   50
 28  \w     86.00 128.00   0.50    0.86    --  114.50 133.00 -53.00   84
 29  \w    100.00 125.00   0.50    0.86    --  114.50 137.00 123.00   50
 30  \w   -175.00-135.00   0.50    0.86    -- -104.00 -77.00 150.00   80
 31  \w    -97.00 -68.00   0.50    0.21    --  -41.23-137.00  60.00   58
 32  \w   -112.00 -87.00   0.50    0.21    --  -41.23-133.00-122.00   50
 33  \w   -122.00 -97.00   0.50    0.86    -- -104.00-133.00-122.00   50
 34  \w   -114.00 -88.00   0.50    0.86    -- -104.00 133.00 -53.00   52
 35  \w    -19.00  36.00   0.50    0.21    --  -41.73  38.00 -90.00  110
 36  \w    -15.00  11.00   0.50    0.21    --  -41.73  19.00-180.00   52
 37  \w    -47.00 -21.00   0.50    0.21    --  -41.73 -77.00   0.00   52
 38  \w   -105.00 -77.00   0.50    0.21    --  -41.73 -77.00   0.00   56
 39  \w    -34.00  29.00   0.50    0.21    --  -41.73  38.00   0.00  126
 40  \w     24.00  65.00   0.50    0.21    --   41.73 -57.00  90.00   82
 41  \w    -14.00  19.00   0.50    0.21    --   41.73 -57.00  90.00   66
 42  \w    -57.00 -32.00   0.50    0.86    -- -104.00 125.00  30.00   50
 43  \w   -124.00 -97.00   0.50    0.86    -- -104.00 143.00  -9.01   54
 44  \w    -67.00 -41.00   0.50    0.86    -- -104.00  61.00 120.00   52
 45  \w     49.00 105.00   0.50    0.86    --  114.50 -95.00   0.00  112
 46  \w     76.00 107.00   0.50    0.86    --  114.50-106.00 -48.72   62
 47  \w     85.00 111.00   0.50    0.86    --  114.50-125.00-150.00   52
 48  \w     73.00 108.00   0.50    0.86    --  114.50-110.00  98.15   70
 49  \w     49.00  91.00   0.50    0.86    --  114.50 -95.00 120.00   84
 50  \w     81.00 108.00   0.50    0.86    --  114.50-125.00 150.00   54
 51  \w     48.00  73.00   0.50    0.86    --  114.50 -61.00 -90.00   50
 52  \w    116.00 175.00   0.50    0.86    --  114.50  15.00-150.00  118
 53  \w     41.00  67.00   0.50    0.86    --  114.50 -61.00 150.00   52
 54  \w     74.00 101.00   0.50    0.86    --  114.50 -95.00 150.00   54
 55  \w     43.00  69.00   0.50    0.86    --  114.50-125.00 150.00   52
 56  \w     41.00  69.00   0.50    0.86    --  114.50 -95.00 150.00   56
 57  \w     41.00  66.00   0.50    0.86    --  114.50 -61.00   0.00   50
 58  \w     44.00  73.00   0.50    0.86    --  114.50-106.00 -48.72   58
 59  \w     75.00 101.00   0.50    0.86    --  114.50 -95.00-180.00   52
 60  \w     45.00  83.00   0.50    0.86    --  114.50 -77.00 -30.00   76
 61  \w    143.00 178.00   0.50    0.86    --  114.50  30.00 -60.00   70
 62  \w     92.00 154.00   0.50    0.86    --  114.50  45.00 150.00  124
 63  \w    104.00 139.00   0.50    0.86    --  114.50  30.00 -60.00   70
 64  \w     86.00 118.00   0.50    0.86    --  114.50 125.00  30.00   64
 65  \w    121.00 175.00   0.50    0.86    --  114.50  61.00 150.00  108
 66  \w    138.00 164.00   0.50    0.86    --  114.50 125.00  30.00   52
 67  \w    130.00 162.00   0.50    0.86    --  114.50  77.00  90.00   64
 68  \w     41.00  66.00   0.50    0.86    --  114.50 -61.00 -60.00   50
 69  \w     42.00  68.00   0.50    0.86    --  114.50 -61.00-180.00   52
 70  \w     46.00  73.00   0.50    0.86    --  114.50 -61.00 120.00   54
 71  \w    -83.00 -58.00   0.50    0.21    --  -41.73 133.00 -53.00   50
 72  \w     78.00 104.00   0.50    0.86    --  114.50 -95.00  30.00   52
 73  \w   -115.00 -13.00   0.50    0.21    --  -41.73 -77.00 120.00  204
 74  \w   -115.00 -19.00   0.50    0.21    --  -41.73 -57.00-150.00  192
 75  \w   -115.00 -13.00   0.50    0.21    --  -41.73 -77.00 -60.00  204
 76  \w     13.00 115.00   0.50    0.21    --   41.73  77.00 -60.00  204
 77  \w     13.00  74.00   0.50    0.21    --   41.73  77.00   0.00  122
 78  \w     13.00 115.00   0.50    0.21    --   41.73  77.00-120.00  204
 79  \w     13.00 115.00   0.50    0.21    --   41.73  77.00-180.00  204
 80  \w     13.00 115.00   0.50    0.21    --   41.73  77.00 120.00  204
 81  \w     20.00 119.00   0.50    0.21    --   41.73  38.00 -90.00  198
 82  \w     25.00 102.00   0.50    0.21    --   41.73-137.00  60.00  154
 83  \w     20.00 119.00   0.50    0.21    --   41.73  38.00  60.00  198
 84  \w     13.00 115.00   0.50    0.21    --   41.73  77.00  60.00  204
 85  \w     37.00  62.00   0.50    0.21    --   41.73-133.00-122.00   50
 86  \w    -67.00 -41.00   0.50    0.86    -- -104.00  61.00  90.00   52
 87  \w    101.00 126.00   0.50    0.86    --  114.50-143.00 -73.32   50
 88  \w    107.00 141.00   0.50    0.86    --  114.50  45.00 -90.00   68
 89  \w     41.00  67.00   0.50    0.86    --  114.50-125.00 -60.00   52
 90  \w     53.00  79.00   0.50    0.86    --  114.50-143.00 -73.32   52
 91  \w   -115.00 -18.00   0.50    0.21    --  -41.73 -65.00 156.98  194
 92  \w   -120.00  37.00   0.50    0.21    --  -41.73   0.00-180.00  314
 93  \w   -120.00  37.00   0.50    0.21    --  -41.73   0.00-150.00  314
 94  \w   -119.00 -18.00   0.50    0.21    --  -41.73 -38.00 -30.00  202
 95  \w     20.00 115.00   0.50    0.21    --   41.73  57.00-180.00  190
 96  \w     13.00 115.00   0.50    0.21    --   41.73  77.00 -90.00  204
 97  \w     20.00 115.00   0.50    0.21    --   41.73  57.00 -60.00  190
 98  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00-180.00  314
 99  \w     20.00 115.00   0.50    0.21    --   41.73  57.00  30.00  190
100  \w     20.00 115.00   0.50    0.21    --   41.73  57.00  60.00  190
101  \w     20.00 119.00   0.50    0.21    --   41.73  38.00-180.00  198
102  \w     20.00 119.00   0.50    0.21    --   41.73  38.00 -60.00  198
103  \w     20.00 119.00   0.50    0.21    --   41.73  38.00 -30.00  198
104  \w     20.00 119.00   0.50    0.21    --   41.73  38.00 120.00  198
105  \w     13.00 115.00   0.50    0.21    --   41.73  77.00  90.00  204
106  \w     20.00 115.00   0.50    0.21    --   41.73  57.00 -30.00  190
107  \w     13.00 115.00   0.50    0.21    --   41.73  77.00 -30.00  204
108  \w     10.00 121.00   0.50    0.21    --   41.73  19.00-150.00  222
109  \w    -38.00  29.00   0.50    0.21    --   41.73 -19.00-150.00  134
110  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00-150.00  314
111  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00-120.00  314
112  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00 -90.00  314
113  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00 -60.00  314
114  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00 -30.00  314
115  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00   0.00  314
116  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00  30.00  314
117  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00  60.00  314
118  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00  90.00  314
119  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00 120.00  314
120  \w    -37.00 120.00   0.50    0.21    --   41.73   0.00 150.00  314
121  \w     20.00 115.00   0.50    0.21    --   41.73  57.00-120.00  190
122  \w     20.00 119.00   0.50    0.21    --   41.73  38.00  90.00  198
123  \w     13.00 115.00   0.50    0.21    --   41.73  77.00 150.00  204
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-DW'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0998209000
_diffrn_orient_matrix_UB_12      -0.0016064000
_diffrn_orient_matrix_UB_13      -0.0891955000
_diffrn_orient_matrix_UB_21      0.0025787000
_diffrn_orient_matrix_UB_22      0.0599586000
_diffrn_orient_matrix_UB_23      -0.0025927000
_diffrn_orient_matrix_UB_31      0.1391522000
_diffrn_orient_matrix_UB_32      0.0000515000
_diffrn_orient_matrix_UB_33      0.0828810000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0948
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            86083
_diffrn_reflns_point_group_measured_fraction_full 0.916
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.251
_diffrn_reflns_theta_min         3.446
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              PhotonJet-DW
_exptl_absorpt_coefficient_mu    8.789
_exptl_absorpt_correction_T_max  0.58896
_exptl_absorpt_correction_T_min  0.55945
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Spherical absorption correction
using equivalent radius and absorption coefficient.
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    1.378
_exptl_crystal_description       plate
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_exptl_crystal_size_rad          0.044
_refine_diff_density_max         3.288
_refine_diff_density_min         -1.590
_refine_diff_density_rms         0.201
_refine_ls_abs_structure_details
;
 Flack x determined using 3171 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.045(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     687
_refine_ls_number_reflns         9843
_refine_ls_number_restraints     1134
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.1336
_refine_ls_R_factor_gt           0.1288
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1553P)^2^+61.8295P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3507
_refine_ls_wR_factor_ref         0.3535
_reflns_Friedel_coverage         0.815
_reflns_Friedel_fraction_full    0.843
_reflns_Friedel_fraction_max     0.842
_reflns_number_gt                9076
_reflns_number_total             9843
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01425h2.cif
_cod_data_source_block           sx21015_2_autored
_cod_depositor_comments          'Adding full bibliography for 7159661.cif.'
_cod_database_code               7159661
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C33 H27 I1 N2 O2'
_shelx_estimated_absorpt_t_max   0.778
_shelx_estimated_absorpt_t_min   0.185
_reflns_odcompleteness_completeness 98.43
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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. Restrained distances
 C16-C13
 1.47 with sigma of 0.02
 C16-C21
 1.37 with sigma of 0.02
 C17-C16 \\sim C18-C17 \\sim C19-C18 \\sim C20-C19 \\sim C21-C20 \\sim C21-C16
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.01 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C4(H4A), C2(H2A), C36(H36), C1(H1A), C3(H3A), C37(H37), C34(H34), C35(H35)
5.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), N4(H4), C40(H40), N2(H2), C9(H9), C28(H28), C24(H24),
 C14(H14), C15(H15), C32(H32), C26(H26), C29(H29), C11(H11), C45(H45), C42(H42),
  C12(H12), C25(H25), C57(H57), C47(H47), C31(H31), C53(H53), C59(H59),
 C58(H58), C61(H61), C48(H48), C7(H7), C54(H54), C44(H44), C17(H17), C62(H62),
 C65(H65), C21(H21), C18(H18), C19(H19), C50(H50), C52(H52), C51(H51), C64(H64),
  C20(H20)
5.c Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C66(H66A,H66B,H66C)
;
_shelx_res_checksum              57571
_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 2.530
_oxdiff_exptl_absorpt_empirical_full_min 0.331