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_1567484
_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         'C20 H16 F2 N2 O3'
_chemical_formula_sum            'C20 H16 F2 N2 O3'
_chemical_formula_weight         370.35
_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     direct
_audit_creation_date             2020-08-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2022-04-01 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                108.139(6)
_cell_angle_beta                 90.02(2)
_cell_angle_gamma                107.606(2)
_cell_formula_units_Z            8
_cell_length_a                   10.4381(4)
_cell_length_b                   17.2549(14)
_cell_length_c                   20.9737(14)
_cell_measurement_reflns_used    8085
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      26.1330
_cell_measurement_theta_min      2.6060
_cell_volume                     3403.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     46.00  92.00   1.00    6.50    --   11.74-178.00-150.00   46
  2  \w    -13.00  58.00   1.00    6.50    --   11.74  37.00  30.00   71
  3  \w    -29.00  87.00   1.00    6.50    --   11.74  19.00 -60.00  116
  4  \w    -47.00  -1.00   1.00    7.00    --  -11.66  88.00-170.00   46
  5  \w    -45.00  -8.00   1.00    7.00    --   11.66 -37.00 -90.00   37
  6  \w     11.00  36.00   1.00    7.00    --   11.66 -37.00 -90.00   25
  7  \w    -21.00  14.00   1.00    7.00    --   11.66  77.00-150.00   35
  8  \w    -19.00  28.00   1.00    7.00    --   11.66  77.00  90.00   47
  9  \w    -13.00  27.00   1.00    7.00    --   11.66  37.00  30.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0326176000
_diffrn_orient_matrix_UB_12      0.0221223000
_diffrn_orient_matrix_UB_13      0.0115648000
_diffrn_orient_matrix_UB_21      -0.0048335000
_diffrn_orient_matrix_UB_22      -0.0196849000
_diffrn_orient_matrix_UB_23      0.0195687000
_diffrn_orient_matrix_UB_31      0.0133995000
_diffrn_orient_matrix_UB_32      -0.0611652000
_diffrn_orient_matrix_UB_33      -0.0021003000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0695
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            11981
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.044
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.113
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84479
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description       needle
_exptl_crystal_F_000             1536
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.357
_refine_diff_density_min         -0.290
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     978
_refine_ls_number_reflns         11981
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0699
_refine_ls_R_factor_gt           0.0493
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0373P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1039
_refine_ls_wR_factor_ref         0.1163
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9157
_reflns_number_total             11981
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03166c2.cif
_cod_data_source_block           8-5
_cod_original_cell_volume        3403.1(4)
_cod_database_code               1567484
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5000(15)
 0.5000(15)
2. 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
3.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C19(H19A,H19B), C39(H39A,H39B), C59(H59A,H59B), C32(H32A,H32B),
 C76(H76A,H76B), C24(H24A,H24B), C89(H89A,H89B)
3.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C5(H5), C14(H14), C2(H2), C12(H12), C3(H3), C4(H4), C6(H6),
 C15(H15), C5BA(H5BA), C35(H35), C2BA(H2BA), C0AA(H0AA), C4AA(H4AA), C29(H29),
 C33(H33), C41(H41), C81(H81), C30(H30), C8AA(H8AA), C27(H27), C1AA(H1AA),
 C2AA(H2AA), C49(H49), C57(H57), C73(H73), C92(H92), C22(H22), C9AA(H9AA),
 C3BA(H3BA), C0BA(H0BA), C4BA(H4BA), C3AA(H3AA), C34(H34), C58(H58), C71(H71)
3.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C5AA(H5AA,H5AB,H5AC), C9BA(H9BA,H9BB,H9BC), C7BA(H7BA,
 H7BB,H7BC)
;
_shelx_res_checksum              52027
_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 1.215
_oxdiff_exptl_absorpt_empirical_full_min 0.793