A Benzyne Insertion Approach to Hetisine-Type Diterpenoid Alkaloids: Synthesis of Cossonidine (Davisine).
Kou, Kevin G. M.; Pflueger, Jason J.; Kiho, Toshihiro; Morrill, Louis C.; Fisher, Ethan L.; Clagg, Kyle; Lebold, Terry P.; Kisunzu, Jessica K.; Sarpong, Richmond; Journal of the American Chemical Society 140 (2018) 8105–8109; doi:10.1021/jacs.8b05043

data_4132595
_publ_section_title
;
 A Benzyne Insertion Approach to Hetisine-Type Diterpenoid Alkaloids:
 Synthesis of Cossonidine (Davisine).
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8105
_journal_page_last               8109
_journal_paper_doi               10.1021/jacs.8b05043
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C H Cl3, C19 H25 N O2'
_chemical_formula_sum            'C20 H26 Cl3 N O2'
_chemical_formula_weight         418.77
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     dual
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7865(2)
_cell_length_b                   12.1566(2)
_cell_length_c                   14.7570(3)
_cell_measurement_reflns_used    13486
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      77.3230
_cell_measurement_theta_min      4.7420
_cell_volume                     1935.04(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0660
_diffrn_reflns_av_unetI/netI     0.0401
_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       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20166
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        68.000
_diffrn_reflns_theta_max         74.490
_diffrn_reflns_theta_min         4.713
_diffrn_source                   'Rotating-anode X-ray tube'
_exptl_absorpt_coefficient_mu    4.389
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70569
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.434
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.070
_exptl_crystal_size_min          0.040
_refine_diff_density_max         0.668
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1521 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.007(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         3954
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0452
_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^)+(0.0639P)^2^+1.8438P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1213
_refine_ls_wR_factor_ref         0.1228
_reflns_Friedel_coverage         0.753
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3764
_reflns_number_total             3954
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b05043_si_003.cif
_cod_data_source_block           kk5_080_minor
_cod_database_code               4132595
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.668
_shelx_estimated_absorpt_t_max   0.844
_shelx_res_checksum              83311
_shelx_hkl_checksum              45370