Cationic Cascade for Building Complex Polycyclic Molecules from Simple Precursors: Diastereoselective Installation of Three Contiguous Stereogenic Centers in a One-Pot Process.
Alachouzos, Georgios; Frontier, Alison J.; Journal of the American Chemical Society 141 (2019) 118–122; doi:10.1021/jacs.8b11713

data_4133616
_publ_section_title
;
 Cationic Cascade for Building Complex Polycyclic Molecules from Simple
 Precursors: Diastereoselective Installation of Three Contiguous
 Stereogenic Centers in a One-Pot Process.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              118
_journal_page_last               122
_journal_paper_doi               10.1021/jacs.8b11713
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C31 H31 N O3'
_chemical_formula_sum            'C31 H31 N O3'
_chemical_formula_weight         465.57
_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             2018-09-26
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                102.743(2)
_cell_angle_beta                 104.147(2)
_cell_angle_gamma                97.677(2)
_cell_formula_units_Z            2
_cell_length_a                   8.2078(2)
_cell_length_b                   9.4326(2)
_cell_length_c                   16.1782(4)
_cell_measurement_reflns_used    19071
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.9800
_cell_measurement_theta_min      2.8880
_cell_volume                     1161.12(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_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    -49.00 -22.00   0.50    0.31    --  -49.75  21.00-109.00   54
  2  \w    -14.00  22.00   0.50    0.31    --  -49.75  21.00-109.00   72
  3  \w    -32.00  16.00   0.50    0.31    --  -49.75  38.00   0.00   96
  4  \w    -49.00 -11.00   0.50    1.24    --  -84.25  21.00-109.00   76
  5  \w    -58.00  22.00   0.50    0.31    --  -44.00  78.00  48.63  160
  6  \w    -36.00  -9.00   0.50    0.31    --    8.00 124.00 115.33   54
  7  \w     -4.00  21.00   0.50    0.31    --   28.00 100.00  71.55   50
  8  \w     17.00  42.00   0.50    0.31    --   44.00  90.00  52.29   50
  9  \w     35.00  63.00   0.50    0.31    --   56.00  78.00  67.29   56
 10  \w     33.00  63.00   0.50    0.31    --   52.00  78.00 111.85   60
 11  \w     50.00  76.00   0.50    0.31    --   68.00  76.00 166.36   52
 12  \w     35.00  61.00   0.50    0.31    --   56.00  77.00 179.23   52
 13  \w     29.00  54.00   0.50    0.31    --   49.75  77.00 150.00   50
 14  \w     86.00 120.00   0.50    1.24    --  105.75  77.00 120.00   68
 15  \w    137.00 174.00   0.50    1.24    --  105.75  77.00  90.00   74
 16  \w    144.00 177.00   0.50    1.24    --  105.75  77.00 150.00   66
 17  \w    136.00 177.00   0.50    1.24    --  105.75  77.00 120.00   82
 18  \w    139.00 164.00   0.50    1.24    --   92.00  76.00  11.92   50
 19  \w    153.00 178.00   0.50    1.24    --  105.75  61.00   0.00   50
 20  \w    135.00 176.00   0.50    1.24    --  105.75  77.00 -30.00   82
 21  \w    133.00 170.00   0.50    1.24    --  105.75  77.00  30.00   74
 22  \w    130.00 176.00   0.50    1.24    --  105.75  77.00  60.00   92
 23  \w    132.00 169.00   0.50    1.24    --  105.75  77.00   0.00   74
 24  \w    140.00 173.00   0.50    1.24    --  105.75  77.00 -60.00   66
 25  \w    147.00 173.00   0.50    1.24    --  105.75  77.00-120.00   52
 26  \w    129.00 154.00   0.50    1.24    --  105.75  21.00-109.00   50
 27  \w    134.00 177.00   0.50    1.24    --  105.75  77.00-150.00   86
 28  \w    103.00 128.00   0.50    0.31    --   56.00  77.00 -61.30   50
 29  \w     82.00 122.00   0.50    0.31    --   49.75  21.00-109.00   80
 30  \w     76.00 101.00   0.50    0.31    --   52.00  75.00 -12.69   50
 31  \w     72.00 115.00   0.50    1.24    --   92.00  76.00  11.92   86
 32  \w     92.00 149.00   0.50    1.24    --  105.75  61.00  60.00  114
 33  \w     94.00 154.00   0.50    1.24    --  105.75  61.00 -30.00  120
 34  \w     93.00 152.00   0.50    1.24    --  105.75  61.00-120.00  118
 35  \w     88.00 178.00   0.50    1.24    --  105.75  77.00 -90.00  180
 36  \w     86.00 114.00   0.50    1.24    --  105.75  77.00  30.00   56
 37  \w     87.00 112.00   0.50    1.24    --  105.75  77.00  90.00   50
 38  \w     98.00 144.00   0.50    1.24    --  105.75  61.00  90.00   92
 39  \w    132.00 158.00   0.50    1.24    --  105.75  61.00 150.00   52
 40  \w     94.00 160.00   0.50    1.24    --  105.75  61.00  30.00  132
 41  \w     92.00 128.00   0.50    1.24    --  105.75  61.00   0.00   72
 42  \w     85.00 115.00   0.50    1.24    --  105.75  77.00 -30.00   60
 43  \w     93.00 147.00   0.50    1.24    --  105.75  61.00 -60.00  108
 44  \w     93.00 156.00   0.50    1.24    --  105.75  61.00-150.00  126
 45  \w     92.00 175.00   0.50    1.24    --  105.75  61.00-180.00  166
 46  \w     94.00 152.00   0.50    1.24    --  105.75  61.00 -90.00  116
 47  \w     91.00 117.00   0.50    1.24    --  105.75  77.00   0.00   52
 48  \w     85.00 110.00   0.50    1.24    --  105.75  77.00  60.00   50
 49  \w     88.00 166.00   0.50    1.24    --  105.75  73.00 106.69  156
 50  \w     86.00 112.00   0.50    1.24    --  105.75  77.00 150.00   52
 51  \w     95.00 127.00   0.50    1.24    --  105.75  61.00 150.00   64
 52  \w     35.00  65.00   0.50    1.24    --  105.75 -21.00  83.00   60
 53  \w     75.00 118.00   0.50    1.24    --  105.75 -61.00  30.00   86
 54  \w     75.00 108.00   0.50    1.24    --  105.75 -94.00   0.00   66
 55  \w     84.00 109.00   0.50    1.24    --  105.75 -94.00  30.00   50
 56  \w     80.00 108.00   0.50    1.24    --  105.75-112.00 -57.91   56
 57  \w     80.00 105.00   0.50    1.24    --  105.75 -94.00-120.00   50
 58  \w     74.00 110.00   0.50    1.24    --  105.75-125.00-150.00   72
 59  \w     71.00 109.00   0.50    1.24    --  105.75 -94.00 -90.00   76
 60  \w     60.00 116.00   0.50    1.24    --  105.75-125.00-180.00  112
 61  \w     46.00  71.00   0.50    1.24    --  105.75 -30.00-120.00   50
 62  \w     43.00 108.00   0.50    1.24    --  105.75 -94.00-150.00  130
 63  \w     50.00 105.00   0.50    1.24    --  105.75 -94.00 -30.00  110
 64  \w     42.00  71.00   0.50    1.24    --  105.75 -94.00   0.00   58
 65  \w     34.00  80.00   0.50    1.24    --  105.75 -94.00  30.00   92
 66  \w     76.00 116.00   0.50    1.24    --  105.75-125.00 120.00   80
 67  \w     34.00  87.00   0.50    1.24    --  105.75 -45.00  30.00  106
 68  \w     45.00  70.00   0.50    1.24    --  105.75 -61.00  30.00   50
 69  \w     37.00  76.00   0.50    1.24    --  105.75-112.00 -57.91   78
 70  \w     34.00  65.00   0.50    1.24    --  105.75 -94.00 -90.00   62
 71  \w     17.00  42.00   0.50    0.31    --   49.75 -21.00  83.00   50
 72  \w     35.00 107.00   0.50    1.24    --  105.75 -61.00 150.00  144
 73  \w     36.00  62.00   0.50    0.31    --   52.00  75.00 -12.69   52
 74  \w     43.00  69.00   0.50    0.31    --   64.00  78.00   4.90   52
 75  \w     37.00  63.00   0.50    0.31    --   56.00  75.00   8.99   52
 76  \w     35.00  70.00   0.50    0.31    --   56.00  77.00 -61.30   70
 77  \w     40.00  71.00   0.50    0.31    --   60.00  76.00-123.71   62
 78  \w     67.00  92.00   0.50    0.31    --   56.00  77.00-142.50   50
 79  \w     36.00  62.00   0.50    0.31    --   56.00  77.00-142.50   52
 80  \w     43.00  76.00   0.50    0.31    --   64.00  77.00-112.73   66
 81  \w     47.00  73.00   0.50    0.31    --   68.00  78.00 -79.43   52
 82  \w     85.00 111.00   0.50    1.24    --  105.75  77.00-120.00   52
 83  \w     85.00 146.00   0.50    1.24    --  105.75  77.00-180.00  122
 84  \w     86.00 125.00   0.50    1.24    --  105.75  77.00-150.00   78
 85  \w     85.00 111.00   0.50    1.24    --  105.75  77.00 -60.00   52
 86  \w     17.00  42.00   0.50    0.31    --   44.00  90.00-173.14   50
 87  \w     11.00  38.00   0.50    0.31    --   36.00  92.00-163.67   54
 88  \w    -16.00  11.00   0.50    0.31    --   16.00 102.00 -83.97   54
 89  \w     17.00  42.00   0.50    0.31    --   44.00  92.00 -50.26   50
 90  \w     -8.00  17.00   0.50    0.31    --   24.00 102.00   6.92   50
 91  \w    -91.00 -11.00   0.50    0.31    --  -49.75 125.00 -90.00  160
 92  \w   -106.00 -81.00   0.50    0.31    --  -49.75 -21.00  83.00   50
 93  \w    -54.00 -29.00   0.50    0.31    --  -49.75 -77.00   0.00   50
 94  \w    -67.00 -42.00   0.50    0.31    --  -64.00 -79.00  84.95   50
 95  \w    -75.00 -49.00   0.50    1.24    --  -68.00 -72.00 101.33   52
 96  \w    -90.00 -65.00   0.50    1.24    --  -80.00 -65.00 169.83   50
 97  \w    -89.00 -64.00   0.50    1.24    --  -84.25 -77.00 120.00   50
 98  \w    -93.00 -68.00   0.50    1.24    --  -84.25 -66.00 119.57   50
 99  \w    -86.00 -61.00   0.50    1.24    --  -84.25 -83.00  86.42   50
100  \w    -88.00 -63.00   0.50    1.24    --  -84.25 -77.00  30.00   50
101  \w    -90.00 -65.00   0.50    1.24    --  -84.25 -77.00 -30.00   50
102  \w    -93.00 -42.00   0.50    0.31    --  -64.00 -79.00 -61.85  102
103  \w    -81.00 -56.00   0.50    1.24    --  -72.00 -67.00 -82.85   50
104  \w    -88.00 -63.00   0.50    1.24    --  -84.25 -77.00-150.00   50
105  \w    -88.00 -63.00   0.50    1.24    --  -84.25 -77.00-120.00   50
106  \w   -105.00 -66.00   0.50    1.24    --  -84.25 -73.00 -47.35   78
107  \w    -95.00 -65.00   0.50    1.24    --  -84.25 -73.00 -88.18   60
108  \w    -89.00 -64.00   0.50    1.24    --  -84.25 -75.00  -9.56   50
109  \w   -100.00 -51.00   0.50    1.24    --  -68.00 -68.00  15.14   98
110  \w    -91.00 -66.00   0.50    1.24    --  -84.25 -71.00  90.03   50
111  \w    -90.00 -65.00   0.50    1.24    --  -84.25 -74.00   7.54   50
112  \w   -105.00 -63.00   0.50    1.24    --  -84.25 -77.00  60.00   84
113  \w    -90.00 -64.00   0.50    1.24    --  -84.25 -76.00 169.13   52
114  \w   -115.00 -63.00   0.50    1.24    --  -84.25 -77.00 150.00  104
115  \w   -141.00-116.00   0.50    1.24    --  -84.25 -21.00  83.00   50
116  \w   -100.00 -63.00   0.50    1.24    --  -80.00 -68.00 -89.71   74
117  \w    -93.00 -68.00   0.50    1.24    --  -84.25 -66.00-116.51   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      -0.1957187000
_diffrn_orient_matrix_UB_12      -0.0543565000
_diffrn_orient_matrix_UB_13      -0.0266121000
_diffrn_orient_matrix_UB_21      -0.0255338000
_diffrn_orient_matrix_UB_22      0.1604064000
_diffrn_orient_matrix_UB_23      0.0058643000
_diffrn_orient_matrix_UB_31      -0.0064964000
_diffrn_orient_matrix_UB_32      -0.0223841000
_diffrn_orient_matrix_UB_33      -0.0980857000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_unetI/netI     0.0288
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            37922
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         78.401
_diffrn_reflns_theta_min         2.920
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.670
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76152
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.332
_exptl_crystal_description       block
_exptl_crystal_F_000             496
_exptl_crystal_size_max          0.117
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.032
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.365
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         4901
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0500
_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^)+(0.0609P)^2^+0.6832P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1322
_refine_ls_wR_factor_ref         0.1374
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4268
_reflns_number_total             4901
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b11713_si_003.cif
_cod_data_source_block           froga20
_cod_database_code               4133616
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C31H31NO3
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.926
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3A)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,
 H18B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C13(H13), C21(H21), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29),
 C30(H30)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              33263
_shelx_hkl_checksum              36980
_olex2_submission_original_sample_id froga20
_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 1.612
_oxdiff_exptl_absorpt_empirical_full_min 0.801