Alkynyl Prins Carbocyclization Cascades for the Synthesis of Linear-Fused Heterocyclic Ring Systems
Hernandez, Jackson; Frontier, Alison; Chemical Science  (2022) –; doi:10.1039/D2SC04750K

data_1567948
_publ_section_title
;
 Alkynyl Prins Carbocyclization Cascades for the Synthesis of Linear-Fused
 Heterocyclic Ring Systems
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04750K
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H27 N O3 S'
_chemical_formula_sum            'C27 H27 N O3 S'
_chemical_formula_weight         445.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-08-08
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-08 deposited with the CCDC.	2022-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.5220(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.17620(10)
_cell_length_b                   11.57040(10)
_cell_length_c                   7.98290(10)
_cell_measurement_reflns_used    25014
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      78.8700
_cell_measurement_theta_min      3.6380
_cell_volume                     1121.158(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.64a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.64a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.64a (Rigaku OD, 2022)'
_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      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    0.23    --  -47.28  19.00-180.00   84
  2  \w    -14.00  28.00   0.50    0.23    --  -47.28  19.00-150.00   84
  3  \w    -14.00  28.00   0.50    0.23    --  -47.28  19.00-120.00   84
  4  \w    -14.00  28.00   0.50    0.23    --  -47.28  19.00 -30.00   84
  5  \w    -14.00  28.00   0.50    0.23    --  -47.28  19.00  60.00   84
  6  \w     25.00 119.00   0.50    0.23    --   47.28  77.00  60.00  188
  7  \w     25.00 119.00   0.50    0.23    --   47.28  77.00  30.00  188
  8  \w     32.00 119.00   0.50    0.23    --   47.28  57.00  30.00  174
  9  \w     25.00 119.00   0.50    0.23    --   47.28  77.00-180.00  188
 10  \w     32.00 119.00   0.50    0.23    --   47.28  57.00 -90.00  174
 11  \w     25.00 119.00   0.50    0.23    --   47.28  77.00 -60.00  188
 12  \w     32.00 119.00   0.50    0.23    --   47.28  57.00 150.00  174
 13  \w    101.00 178.00   0.50    0.91    --  113.25  45.00 150.00  154
 14  \w    101.00 178.00   0.50    0.91    --  113.25  30.00 150.00  154
 15  \w    101.00 178.00   0.50    0.91    --  113.25  30.00  90.00  154
 16  \w    100.00 178.00   0.50    0.91    --  113.25  15.00  30.00  156
 17  \w    100.00 178.00   0.50    0.91    --  113.25  15.00 -30.00  156
 18  \w    100.00 178.00   0.50    0.91    --  113.25  15.00-120.00  156
 19  \w     93.00 178.00   0.50    0.91    --  113.25 129.00-138.00  170
 20  \w     95.00 178.00   0.50    0.91    --  113.25 125.00-120.00  166
 21  \w     42.00  76.00   0.50    0.91    --  113.25 -61.00 120.00   68
 22  \w     42.00  76.00   0.50    0.91    --  113.25 -61.00 -30.00   68
 23  \w     42.00  76.00   0.50    0.91    --  113.25 -61.00 -90.00   68
 24  \w     42.00  76.00   0.50    0.91    --  113.25 -61.00-150.00   68
 25  \w     42.00 106.00   0.50    0.91    --  113.25 -94.00-120.00  128
 26  \w     43.00 104.00   0.50    0.23    --   47.28-141.00 -24.00  122
 27  \w     43.00 123.00   0.50    0.91    --  113.25-141.00 -24.00  160
 28  \w     42.00 106.00   0.50    0.91    --  113.25 -94.00 -30.00  128
 29  \w     44.00 111.00   0.50    0.91    --  113.25-125.00  60.00  134
 30  \w     43.00 114.00   0.50    0.91    --  113.25-129.00 147.00  142
 31  \w     42.00 106.00   0.50    0.91    --  113.25 -94.00 150.00  128
 32  \w     37.00  96.00   0.50    0.23    --   47.28-129.00 147.00  118
 33  \w    -47.00 -20.00   0.50    0.91    --  -91.75  45.00-150.00   54
 34  \w    -89.00 -15.00   0.50    0.23    --  -47.28 129.00-138.00  148
 35  \w    -98.00 -21.00   0.50    0.91    --  -91.75 141.00  33.00  154
 36  \w    -47.00 -20.00   0.50    0.91    --  -91.75  45.00-120.00   54
 37  \w   -163.00 -69.00   0.50    0.91    --  -91.75 -77.00 -90.00  188
 38  \w   -119.00 -63.00   0.50    0.23    --  -47.28-141.00 -24.00  112
 39  \w   -118.00 -71.00   0.50    0.23    --  -47.28-129.00 147.00   94
 40  \w   -162.00 -71.00   0.50    0.91    --  -91.75-129.00 147.00  182
 41  \w    -61.00 -30.00   0.50    0.91    --  -91.75 143.00 -57.00   62
 42  \w    -78.00 -36.00   0.50    0.23    --  -47.28 -37.00 -30.00   84
 43  \w    -60.00 -35.00   0.50    0.23    --  -47.28 -37.00  30.00   50
 44  \w     65.00  95.00   0.50    0.23    --   47.28  19.00 120.00   60
 45  \w     25.00  50.00   0.50    0.23    --   47.28  77.00 150.00   50
 46  \w     25.00  53.00   0.50    0.23    --   47.28  77.00-120.00   56
 47  \w     26.00  52.00   0.50    0.23    --   47.28  77.00   0.00   52
 48  \w     35.00  63.00   0.50    0.23    --   47.28  19.00 120.00   56
 49  \w     35.00  62.00   0.50    0.23    --   47.28  57.00  90.00   54
 50  \w     28.00  54.00   0.50    0.23    --   47.28  77.00  90.00   52
 51  \w     33.00  60.00   0.50    0.23    --   47.28  57.00-180.00   54
 52  \w    -98.00 -72.00   0.50    0.91    --  -91.75 -73.00  69.08   52
 53  \w    -95.00 -69.00   0.50    0.91    --  -91.75 -77.00 150.00   52
 54  \w    -96.00 -70.00   0.50    0.91    --  -91.75 -77.00 120.00   52
 55  \w    -95.00 -69.00   0.50    0.91    --  -91.75 -77.00  30.00   52
 56  \w    -97.00 -71.00   0.50    0.91    --  -91.75 -77.00-161.45   52
 57  \w   -101.00 -71.00   0.50    0.91    --  -91.75 -75.00  42.83   60
 58  \w   -101.00 -75.00   0.50    0.91    --  -91.75 -62.00 -88.98   52
 59  \w    -95.00 -69.00   0.50    0.91    --  -91.75 -76.00-116.90   52
 60  \w   -102.00 -76.00   0.50    0.91    --  -91.75 -59.00-124.29   52
 61  \w    -94.00 -69.00   0.50    0.91    --  -91.75 -76.00 138.08   50
 62  \w    -94.00 -69.00   0.50    0.91    --  -91.75 -76.00-132.50   50
 63  \w    -95.00 -69.00   0.50    0.91    --  -91.75 -76.00  16.89   52
 64  \w    -97.00 -71.00   0.50    0.91    --  -91.75 -71.00 -30.41   52
 65  \w    -97.00 -71.00   0.50    0.91    --  -91.75 -77.00 -30.00   52
 66  \w    -99.00 -73.00   0.50    0.91    --  -91.75 -67.00 -56.90   52
 67  \w   -110.00 -69.00   0.50    0.91    --  -91.75 -77.00 -60.00   82
 68  \w   -142.00-116.00   0.50    0.91    --  -91.75 -77.00  90.00   52
 69  \w    -95.00 -69.00   0.50    0.91    --  -91.75 -77.00-150.00   52
 70  \w    -94.00 -69.00   0.50    0.91    --  -91.75 -77.00  90.00   50
 71  \w    -94.00 -69.00   0.50    0.91    --  -91.75 -77.00   0.00   50
 72  \w    -95.00 -69.00   0.50    0.91    --  -91.75 -77.00-180.00   52
 73  \w   -138.00-112.00   0.50    0.91    --  -91.75 -76.00 138.08   52
 74  \w    -95.00 -70.00   0.50    0.91    --  -91.75 -74.00  65.37   50
 75  \w    -95.00 -69.00   0.50    0.91    --  -91.75 -76.00 165.37   52
 76  \w    -94.00 -69.00   0.50    0.91    --  -91.75 -76.00 105.94   50
 77  \w   -101.00 -75.00   0.50    0.91    --  -91.75 -62.00 -31.82   52
 78  \w    -97.00 -71.00   0.50    0.91    --  -91.75 -77.00  60.00   52
 79  \w     45.00  71.00   0.50    0.91    --  113.25-125.00 120.00   52
 80  \w    138.00 168.00   0.50    0.91    --  113.25 143.00 -57.00   60
 81  \w     97.00 131.00   0.50    0.91    --  113.25  61.00-120.00   68
 82  \w    153.00 178.00   0.50    0.91    --  113.25  77.00 150.00   50
 83  \w    109.00 135.00   0.50    0.91    --  113.25 143.00 -57.00   52
 84  \w     98.00 131.00   0.50    0.91    --  113.25  61.00-180.00   66
 85  \w     91.00 121.00   0.50    0.91    --  113.25  77.00 150.00   60
 86  \w    100.00 146.00   0.50    0.91    --  113.25  61.00 -60.00   92
 87  \w    141.00 174.00   0.50    0.91    --  113.25  77.00  90.00   66
 88  \w     42.00  92.00   0.50    0.91    --  113.25 -94.00-150.00  100
 89  \w     92.00 147.00   0.50    0.91    --  113.25  77.00-150.00  110
 90  \w    102.00 137.00   0.50    0.91    --  113.25  45.00  90.00   70
 91  \w     92.00 131.00   0.50    0.91    --  113.25  77.00   0.00   78
 92  \w     91.00 117.00   0.50    0.91    --  113.25  77.00  90.00   52
 93  \w     91.00 122.00   0.50    0.91    --  113.25  77.00-180.00   62
 94  \w     91.00 117.00   0.50    0.91    --  113.25  77.00 120.00   52
 95  \w    135.00 163.00   0.50    0.91    --  113.25  77.00 120.00   56
 96  \w     81.00 107.00   0.50    0.91    --  113.25-125.00  30.00   52
 97  \w     98.00 127.00   0.50    0.91    --  113.25  61.00-150.00   58
 98  \w     48.00  75.00   0.50    0.91    --  113.25-125.00  30.00   54
 99  \w    153.00 178.00   0.50    0.91    --  113.25  61.00   0.00   50
100  \w    134.00 164.00   0.50    0.91    --  113.25  77.00  30.00   60
101  \w     91.00 128.00   0.50    0.91    --  113.25  77.00  30.00   74
102  \w     97.00 135.00   0.50    0.91    --  113.25  61.00   0.00   76
103  \w    141.00 172.00   0.50    0.91    --  113.25  61.00 -30.00   62
104  \w     98.00 141.00   0.50    0.91    --  113.25  77.00-120.00   86
105  \w    103.00 131.00   0.50    0.91    --  113.25  61.00 -30.00   56
106  \w     48.00  75.00   0.50    0.91    --  113.25 -77.00-120.00   54
107  \w    134.00 160.00   0.50    0.91    --  113.25  77.00 -90.00   52
108  \w    131.00 177.00   0.50    0.91    --  113.25  77.00 -60.00   92
109  \w     92.00 118.00   0.50    0.91    --  113.25  77.00 -90.00   52
110  \w     92.00 118.00   0.50    0.91    --  113.25  77.00 -60.00   52
111  \w     99.00 126.00   0.50    0.91    --  113.25  61.00 150.00   54
112  \w    102.00 128.00   0.50    0.91    --  113.25  61.00  60.00   52
113  \w     87.00 114.00   0.50    0.91    --  113.25 -77.00-120.00   54
114  \w     43.00  86.00   0.50    0.91    --  113.25 -94.00  60.00   86
115  \w     76.00 103.00   0.50    0.91    --  113.25-125.00 120.00   54
116  \w    150.00 176.00   0.50    0.91    --  113.25  61.00-180.00   52
117  \w     42.00  67.00   0.50    0.91    --  113.25 -61.00  30.00   50
;
_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      0.0102226000
_diffrn_orient_matrix_UB_12      -0.1325632000
_diffrn_orient_matrix_UB_13      0.0109854000
_diffrn_orient_matrix_UB_21      -0.1262828000
_diffrn_orient_matrix_UB_22      -0.0111305000
_diffrn_orient_matrix_UB_23      -0.0255024000
_diffrn_orient_matrix_UB_31      0.0072382000
_diffrn_orient_matrix_UB_32      -0.0060622000
_diffrn_orient_matrix_UB_33      -0.1915817000
_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  0.0717
_diffrn_reflns_av_unetI/netI     0.0369
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            34948
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.188
_diffrn_reflns_theta_min         3.641
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.516
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62538
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.64a (Rigaku Oxford Diffraction, 2022)
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       needle
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.489
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.383
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 1972 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.002(16)
_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     290
_refine_ls_number_reflns         4549
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0806P)^2^+0.2718P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1208
_refine_ls_wR_factor_ref         0.1219
_reflns_Friedel_coverage         0.870
_reflns_Friedel_fraction_full    0.895
_reflns_Friedel_fraction_max     0.865
_reflns_number_gt                4400
_reflns_number_total             4549
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04750k2.cif
_cod_data_source_block           frojjh31
_cod_database_code               1567948
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.524
_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 Ternary CH refined with riding coordinates:
 C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C6(H6A,H6B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C16(H16), C17(H17), C18(H18), C19(H19),
 C20(H20), C22(H22), C23(H23), C25(H25), C26(H26)
2.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C)
;
_shelx_res_checksum              96831
_shelx_hkl_checksum              98638
_olex2_submission_original_sample_id frojjh31
_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 1.611
_oxdiff_exptl_absorpt_empirical_full_min 0.519