Zn(OTf)2-mediated annulations of N-propargylated tetrahydrocarbolines: divergent synthesis of four distinct alkaloidal scaffolds
Yorimoto, Sadaiwa; Tsubouchi, Akira; Mizoguchi, Haruki; Oikawa, Hideaki; Tsunekawa, Yoshiaki; Ichino, Tomoya; Maeda, Satoshi; Oguri, Hiroki; Chemical Science  (2019) –; doi:10.1039/C9SC01507H

data_1550965
_publ_section_title
;
 Zn(OTf)2-mediated annulations of N-propargylated tetrahydrocarbolines:
 divergent synthesis of four distinct alkaloidal scaffolds
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC01507H
_journal_year                    2019
_chemical_formula_moiety         'C23 H23 N3 O, 0.5(C4 H8 O2)'
_chemical_formula_sum            'C24 H24 N4 O2.5'
_chemical_formula_weight         408.47
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-08
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-03-27 deposited with the CCDC.    2019-04-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.133(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3214(12)
_cell_length_b                   8.4434(8)
_cell_length_c                   20.5045(17)
_cell_measurement_reflns_used    3901
_cell_measurement_temperature    170
_cell_measurement_theta_max      27.9780
_cell_measurement_theta_min      2.6240
_cell_volume                     2106.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170
_diffrn_detector_area_resol_mean 6.83
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.918
_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    -74.00 119.00   1.00   58.26    --   30.00  54.00-180.00  193
  2  \w     16.00 119.00   1.00   58.26    --   30.00  54.00-180.00  103
  3  \w      6.00 115.00   1.00   58.26    --   30.00  54.00  90.00  109
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini (JP)'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0014728000
_diffrn_orient_matrix_UB_12      -0.0136645000
_diffrn_orient_matrix_UB_13      0.0342479000
_diffrn_orient_matrix_UB_21      0.0582366000
_diffrn_orient_matrix_UB_22      0.0043868000
_diffrn_orient_matrix_UB_23      0.0049915000
_diffrn_orient_matrix_UB_31      -0.0028861000
_diffrn_orient_matrix_UB_32      0.0827383000
_diffrn_orient_matrix_UB_33      0.0054782000
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0658
_diffrn_reflns_av_unetI/netI     0.1350
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.918
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21973
_diffrn_reflns_point_group_measured_fraction_full 0.959
_diffrn_reflns_point_group_measured_fraction_max 0.816
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.024
_diffrn_reflns_theta_min         2.614
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97053
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.842
_refine_diff_density_min         -0.510
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 1265 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -4.5(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         12924
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.1865
_refine_ls_R_factor_gt           0.0875
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2126
_refine_ls_wR_factor_ref         0.2969
_reflns_Friedel_coverage         0.679
_reflns_Friedel_fraction_full    0.913
_reflns_Friedel_fraction_max     0.700
_reflns_number_gt                5418
_reflns_number_total             12924
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc01507h2.cif
_cod_data_source_block           20190307at345-1
_cod_original_formula_sum        'C24 H24 N4 O2.50'
_cod_database_code               1550965
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C00O(H00A,H00B), C00X(H00F,H00G), C00Y(H00H,H00I), C010(H01P,H01Q), C013(H01R,
 H01S), C014(H01A,H01B), C019(H01C,H01D), C01E(H01K,H01L), C01M(H01W,H01X)
2.b Aromatic/amide H refined with riding coordinates:
 N002(H002), N004(H004), N005(H005), N008(H008), C00M(H00M), C00U(H00U),
 C00V(H00V), C00W(H00W), C00Z(H00Z), C011(H011), C012(H012), C015(H015),
 C016(H016), C017(H017), C018(H018), C01A(H01E), C01B(H01F), C01C(H01G),
 C01F(H01M), C01G(H01N), C01I(H01T), C01J(H01U), C01K(H01V), C01L(H01O)
2.c Idealised Me refined as rotating group:
 C00T(H00C,H00D,H00E), C01D(H01H,H01I,H01J), C01N(H01Y,H,HA), C01O(H01Z,HB,HC)
;
_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 1.061
_oxdiff_exptl_absorpt_empirical_full_min 0.911