Base-Promoted Cascade β-F-Elimination/Electrocyclization/Diels-Alder/Retro-Diels-Alder Reaction: Efficient Access to δ-Carboline Derivatives
Sun, Xi-Shang; Diao, Xin-Yu; Dong, Xiu-Qin; Wang, Chun-Jiang; Chemical Science  (2022) –; doi:10.1039/D2SC03166C

data_1567483
_publ_section_title
;
 Base-Promoted Cascade
 \b-F-Elimination/Electrocyclization/Diels-Alder/Retro-Diels-Alder
 Reaction: Efficient Access to \d-Carboline Derivatives
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC03166C
_journal_year                    2022
_chemical_formula_moiety         'C21 H18 N2 O2'
_chemical_formula_sum            'C21 H18 N2 O2'
_chemical_formula_weight         330.37
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-03
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2022-04-01 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                85.805(2)
_cell_angle_beta                 74.493(3)
_cell_angle_gamma                77.630(2)
_cell_formula_units_Z            2
_cell_length_a                   8.0404(2)
_cell_length_b                   9.2472(3)
_cell_length_c                   11.6115(4)
_cell_measurement_reflns_used    13491
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.5930
_cell_measurement_theta_min      3.9450
_cell_volume                     812.47(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.975
_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    -28.00  28.00   0.50    0.50    --    0.00 -82.00   0.00  112
  2  \w    -15.00  11.00   0.50    0.50    --   32.00 -54.00  73.92   52
  3  \w    -49.00 -16.00   0.50    0.50    --   32.00 -54.00  73.92   66
  4  \w     14.00  42.00   0.50    0.50    --   32.00  72.00  87.39   56
  5  \w     18.00  53.00   0.50    0.50    --   32.00 -54.00  73.92   70
  6  \w     86.00 121.00   0.50    0.50    --   40.00  72.00 -61.17   70
  7  \w     19.00  45.00   0.50    0.50    --   40.00  72.00 -61.17   52
  8  \w     21.00  49.00   0.50    0.50    --   48.00  72.00   0.92   56
  9  \w     26.00  58.00   0.50    0.50    --   52.00  69.00-158.69   64
 10  \w     32.00  63.00   0.50    0.50    --   56.00  75.00 -46.67   62
 11  \w     29.00  55.00   0.50    0.50    --   56.00  73.00 126.18   52
 12  \w     61.00  87.00   0.50    0.50    --   56.00  73.00 126.18   52
 13  \w     81.00 107.00   0.50    0.50    --   60.00  75.00  27.91   52
 14  \w     33.00  64.00   0.50    0.50    --   60.00  75.00  27.91   62
 15  \w     37.00  87.00   0.50    0.50    --   64.00  73.00 -87.40  100
 16  \w     37.00  96.00   0.50    0.50    --   64.00  75.00-129.56  118
 17  \w     42.00  97.00   0.50    0.50    --   64.00  73.00  54.96  110
 18  \w     39.00  73.00   0.50    0.50    --   64.00  74.00-165.45   68
 19  \w     81.00 107.00   0.50    0.50    --   68.00  75.00 150.44   52
 20  \w     40.00  78.00   0.50    0.50    --   68.00  75.00 150.44   76
 21  \w     40.00  65.00   0.50    0.50    --   68.00  74.00  88.76   50
 22  \w     47.00  78.00   0.50    0.50    --   72.00  73.00 111.58   62
 23  \w     46.00  72.00   0.50    0.50    --   72.00  71.00 -31.77   52
 24  \w    122.00 161.00   0.50    0.50    --   72.00  71.00 -31.77   78
 25  \w    123.00 169.00   0.50    0.50    --   80.00  74.00  -5.77   92
 26  \w     52.00  83.00   0.50    0.50    --   80.00  74.00  -5.77   62
 27  \w     65.00 145.00   0.50    0.50    --   88.00  64.00-130.78  160
 28  \w     26.00  66.00   0.50    0.50    --   94.60 -82.00 -90.00   80
 29  \w    136.00 162.00   0.50    0.50    --   94.60  61.00-180.00   52
 30  \w     69.00 143.00   0.50    0.50    --   94.60  68.00 -74.18  148
 31  \w     71.00 124.00   0.50    0.50    --   94.60  61.00-180.00  106
 32  \w     32.00  76.00   0.50    0.50    --   94.60 -82.00 120.00   88
 33  \w    149.00 184.00   0.50    0.50    --   94.60  61.00   0.00   70
 34  \w    149.00 183.00   0.50    0.50    --   94.60  61.00  90.00   68
 35  \w     71.00 127.00   0.50    0.50    --   94.60  61.00  90.00  112
 36  \w     72.00 127.00   0.50    0.50    --   94.60  61.00 -30.00  110
 37  \w     67.00 121.00   0.50    0.50    --   94.60 -82.00  90.00  108
 38  \w     31.00  59.00   0.50    0.50    --   94.60 -82.00  90.00   56
 39  \w     75.00 101.00   0.50    0.50    --   94.60 -30.00 -30.00   52
 40  \w      5.00  70.00   0.50    0.50    --   94.60 -30.00 -30.00  130
 41  \w     68.00 167.00   0.50    0.50    --   94.60  70.00 -96.97  198
 42  \w     72.00 181.00   0.50    0.50    --   94.60  61.00-150.00  218
 43  \w     65.00 125.00   0.50    0.50    --   94.60 -82.00-180.00  120
 44  \w      5.00  60.00   0.50    0.50    --   94.60 -82.00-180.00  110
 45  \w     73.00 101.00   0.50    0.50    --   94.60 -61.00 -90.00   56
 46  \w      6.00  53.00   0.50    0.50    --   94.60 -61.00 -90.00   94
 47  \w     88.00 121.00   0.50    0.50    --   94.60 -82.00 -30.00   66
 48  \w    139.00 184.00   0.50    0.50    --   94.60  61.00 120.00   90
 49  \w      6.00  31.00   0.50    0.50    --   94.60 -82.00 -30.00   50
 50  \w     72.00 129.00   0.50    0.50    --   94.60  61.00 120.00  114
 51  \w     67.00 112.00   0.50    0.50    --   94.60  72.00  22.70   90
 52  \w     75.00 127.00   0.50    0.50    --   94.60  61.00 150.00  104
 53  \w    147.00 179.00   0.50    0.50    --   94.60  61.00 -30.00   64
 54  \w     74.00 121.00   0.50    0.50    --   94.60  61.00   0.00   94
 55  \w     71.00 143.00   0.50    0.50    --   94.60  61.00  60.00  144
 56  \w     75.00 126.00   0.50    0.50    --   94.60 -82.00 -90.00  102
 57  \w     97.00 123.00   0.50    0.50    --   94.60 -82.00 120.00   52
 58  \w    156.00 181.00   0.50    0.50    --   94.60  68.00 -74.18   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0657584000
_diffrn_orient_matrix_UB_12      0.0591120000
_diffrn_orient_matrix_UB_13      0.1283457000
_diffrn_orient_matrix_UB_21      0.1294659000
_diffrn_orient_matrix_UB_22      -0.1285800000
_diffrn_orient_matrix_UB_23      0.0408372000
_diffrn_orient_matrix_UB_31      0.1419299000
_diffrn_orient_matrix_UB_32      0.0952428000
_diffrn_orient_matrix_UB_33      -0.0286846000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0177
_diffrn_reflns_av_unetI/netI     0.0102
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            16032
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.854
_diffrn_reflns_theta_min         3.951
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.702
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_description       plate
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.307
_refine_diff_density_min         -0.187
_refine_diff_density_rms         0.041
_refine_ls_extinction_coef       0.0116(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         3208
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0326
_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^)+(0.0383P)^2^+0.3378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0819
_refine_ls_wR_factor_ref         0.0822
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3142
_reflns_number_total             3208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03166c2.cif
_cod_data_source_block           20200903_sxs-9-3
_cod_database_code               1567483
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.766
_reflns_odcompleteness_completeness 99.62
_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:
 C00H(H00B,H00C)
2.b Aromatic/amide H refined with riding coordinates:
 C006(H006), C00A(H00A), C00E(H00E), C00F(H00F), C00G(H00G), C00J(H00J),
 C00K(H00K), C00L(H00L), C00M(H00M), C00O(H00O)
2.c Idealised Me refined as rotating group:
 C00N(H00D,H00H,H00I), C00P(H00N,H00P,H00Q)
;
_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 1.751
_oxdiff_exptl_absorpt_empirical_full_min 0.576