Total Synthesis of (+)-Granatumine A and Related Bislactone Limonoid Alkaloids via a Pyran to Pyridine Interconversion.
Schuppe, Alexander W.; Zhao, Yizhou; Liu, Yannan; Newhouse, Timothy R.; Journal of the American Chemical Society 141 (2019) 9191–9196; doi:10.1021/jacs.9b04508

data_4128753
_publ_section_title
;
 Total Synthesis of (+)-Granatumine A and Related Bislactone Limonoid
 Alkaloids via a Pyran to Pyridine Interconversion.
;
_journal_issue                   23
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9191
_journal_page_last               9196
_journal_paper_doi               10.1021/jacs.9b04508
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H27 N O6'
_chemical_formula_sum            'C26 H27 N O6'
_chemical_formula_weight         449.48
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     SHELXT
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                89.972(3)
_cell_angle_beta                 69.566(4)
_cell_angle_gamma                79.485(4)
_cell_formula_units_Z            2
_cell_length_a                   9.3675(4)
_cell_length_b                   9.8446(4)
_cell_length_c                   12.9472(6)
_cell_measurement_reflns_used    34099
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      66.5400
_cell_measurement_theta_min      3.6130
_cell_volume                     1097.47(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB-2014/2 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT-2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector_area_resol_mean 22.2
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Rigaku Saturn 944+ CCD'
_diffrn_measurement_method       \w
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_av_unetI/netI     0.0164
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            37852
_diffrn_reflns_point_group_measured_fraction_full 0.938
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         3.652
_diffrn_source                   'microfocus rotating anode'
_exptl_absorpt_coefficient_mu    0.793
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81684
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
CrysAlisPro 1.171.39.16b (Rigaku Oxford Diffraction, 2015) 
Empirical absorption correction using spherical harmonics, 
 implemented in SCALE3 ABSPACK scaling algorithm. 
;
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       Block
_exptl_crystal_F_000             476
_exptl_crystal_size_max          0.040
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.040
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
; 
 Flack x determined using 3341 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.01(5)
_refine_ls_extinction_coef       0.0140(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     612
_refine_ls_number_reflns         7289
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0284
_refine_ls_R_factor_gt           0.0280
_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^)+(0.0442P)^2^+0.1626P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0701
_refine_ls_wR_factor_ref         0.0704
_reflns_Friedel_coverage         0.905
_reflns_Friedel_fraction_full    0.891
_reflns_Friedel_fraction_max     0.891
_reflns_number_gt                7198
_reflns_number_total             7289
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04508_si_002.cif
_cod_data_source_block           007b-19038
_cod_database_code               4128753
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.969
_shelx_estimated_absorpt_t_max   0.969
_shelx_res_checksum              34872
_shelx_hkl_checksum              20132