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_4128752
_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         'C11 H14 O4, 0.5(C H Cl3), 0.5(H2 O)'
_chemical_formula_sum            'C11.5 H15.5 Cl1.5 O4.5'
_chemical_formula_weight         278.91
_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   mixed
_atom_sites_solution_primary     SHELXT
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.1874(2)
_cell_length_b                   13.9904(2)
_cell_length_c                   20.1638(3)
_cell_measurement_reflns_used    46851
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      66.3670
_cell_measurement_theta_min      3.1910
_cell_volume                     2591.76(8)
_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 0.993
_diffrn_measured_fraction_theta_max 0.992
_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  0.0534
_diffrn_reflns_av_unetI/netI     0.0156
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            90384
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        66.790
_diffrn_reflns_theta_max         66.790
_diffrn_reflns_theta_min         3.846
_diffrn_source                   'microfocus rotating anode'
_exptl_absorpt_coefficient_mu    3.634
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82031
_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    1.430
_exptl_crystal_description       plate
_exptl_crystal_F_000             1168
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.080
_refine_diff_density_max         0.337
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
; 
 Flack x determined using 1790 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.000(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         4568
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0329
_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^)+(0.0472P)^2^+0.9497P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0827
_refine_ls_wR_factor_ref         0.0842
_reflns_Friedel_coverage         0.761
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4339
_reflns_number_total             4568
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b04508_si_003.cif
_cod_data_source_block           007a-18052
_cod_original_formula_sum        'C11.50 H15.50 Cl1.50 O4.50'
_cod_database_code               4128752
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.530
_shelx_estimated_absorpt_t_max   0.760
_shelx_res_checksum              8621
_shelx_hkl_checksum              99847