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_4133642
_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_formula_moiety         'C20 H22 Br N3 O7'
_chemical_formula_sum            'C20 H22 Br N3 O7'
_chemical_formula_weight         496.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_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                90
_cell_angle_beta                 105.487(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4462(5)
_cell_length_b                   16.5828(8)
_cell_length_c                   12.4288(6)
_cell_measurement_reflns_used    9870
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.30
_cell_measurement_theta_min      2.37
_cell_volume                     2074.83(17)
_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      99.99
_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 0.996
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0162
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            59597
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.358
_diffrn_reflns_theta_min         2.097
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.030
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5133
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0930 before and 0.0571 after correction. The Ratio of minimum to maximum transmission is 0.6883. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.589
_exptl_crystal_description       prism
_exptl_crystal_F_000             1016
_exptl_crystal_recrystallization_method
'The crystallization was done with 1:1 racemic mixture using dichloromethane/hexane co-solvent at rt.'
_exptl_crystal_size_max          0.614
_exptl_crystal_size_mid          0.569
_exptl_crystal_size_min          0.521
_refine_diff_density_max         0.425
_refine_diff_density_min         -0.517
_refine_diff_density_rms         0.067
_refine_ls_extinction_coef       0.0212(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   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     285
_refine_ls_number_reflns         5161
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0277
_refine_ls_R_factor_gt           0.0253
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0324P)^2^+1.5629P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0642
_refine_ls_wR_factor_ref         0.0655
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4826
_reflns_number_total             5161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12123_si_004.cif
_cod_data_source_block           dd43ks
_cod_database_code               4133642
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.418
_shelx_estimated_absorpt_t_min   0.369
_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 C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C18(H18)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              63277
_shelx_hkl_checksum              62113
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with spindle axis of 1 -1 0.'
_olex2_submission_original_sample_id TWB-epoxyaceonide
_olex2_submission_special_instructions 'No special instructions were received'