Enantioselective Synthesis of Isocarbostyril Alkaloids and Analogs Using Catalytic Dearomative Functionalization of Benzene.
Bingham, Tanner W.; Hernandez, Lucas W.; Olson, Daniel G.; Svec, Riley L.; Hergenrother, Paul J.; Sarlah, David; Journal of the American Chemical Society 141 (2019) 657–670; doi:10.1021/jacs.8b12123

data_4133645
_publ_section_title
;
 Enantioselective Synthesis of Isocarbostyril Alkaloids and Analogs Using
 Catalytic Dearomative Functionalization of Benzene.
;
_journal_issue                   1
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              657
_journal_page_last               670
_journal_paper_doi               10.1021/jacs.8b12123
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H13 N O6, H2 O'
_chemical_formula_sum            'C14 H15 N O7'
_chemical_formula_weight         309.27
_chemical_name_systematic        (+)-lycoricidine
_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     dual
_audit_creation_date             2018-05-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                67.5140(10)
_cell_angle_beta                 89.8880(10)
_cell_angle_gamma                75.5250(10)
_cell_formula_units_Z            2
_cell_length_a                   7.2381(3)
_cell_length_b                   9.3207(4)
_cell_length_c                   11.0024(4)
_cell_measurement_reflns_used    18364
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.15
_cell_measurement_theta_min      4.37
_cell_volume                     660.42(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_detector                 'Bruker Photon 100 area detector'
_diffrn_detector_type            'photon counter area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture/Photon 100'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            18788
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.230
_diffrn_reflns_theta_min         4.373
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.081
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6327
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0851 before and 0.0468 after correction. The Ratio of minimum to maximum transmission is 0.8401. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.555
_exptl_crystal_description       plate
_exptl_crystal_F_000             324
_exptl_crystal_recrystallization_method
'Recrystalization was done with enantiopure material (>99% ee) using methanol/water co-solvent at rt.'
_exptl_crystal_size_max          0.333
_exptl_crystal_size_mid          0.317
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.281
_refine_diff_density_rms         0.090
_refine_ls_abs_structure_details
;
 Flack x determined using 2213 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(8)
_refine_ls_extinction_coef       0.062(3)
_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   1.072
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         4675
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0497P)^2^+0.1780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0778
_refine_ls_wR_factor_ref         0.0780
_reflns_Friedel_coverage         0.937
_reflns_Friedel_fraction_full    0.937
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                4632
_reflns_number_total             4675
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12123_si_002.cif
_cod_data_source_block           cu_dd85l_0m
_cod_database_code               4133645
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.855
_shelx_estimated_absorpt_t_min   0.715
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All N(H) groups, All O(H) groups, All O(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2B), C3(H3A), C4(H4A), C5(H5), C16(H16), C17(H17), C18(H18), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C7(H7), C10(H10A), C15(H15), C21(H21), C24(H24)
;
_shelx_res_checksum              21894
_shelx_hkl_checksum              16281
_olex2_exptl_crystal_mounting_method
'the crystal was mounted on a loop with spindle axis of -1 2 3'
_olex2_submission_original_sample_id (+)-lycoricidine
_olex2_submission_special_instructions 'No special instructions were received'