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_4133643
_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         'C17 H17 Br2 N3 O5'
_chemical_formula_sum            'C17 H17 Br2 N3 O5'
_chemical_formula_weight         503.15
_chemical_name_systematic        halohydrin
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.6830(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6131(2)
_cell_length_b                   13.0876(4)
_cell_length_c                   16.5039(5)
_cell_measurement_reflns_used    9891
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.31
_cell_measurement_theta_min      2.85
_cell_volume                     1843.70(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      100.15
_diffrn_detector                 'Bruker APEXII CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0246
_diffrn_reflns_av_unetI/netI     0.0173
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            24215
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.341
_diffrn_reflns_theta_min         2.849
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Siemens fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.432
_exptl_absorpt_correction_T_max  0.6275
_exptl_absorpt_correction_T_min  0.3439
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'TWINABS-2012/1 (Bruker,2012) was used for absorption correction.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.813
_exptl_crystal_description       prism
_exptl_crystal_F_000             1000
_exptl_crystal_recrystallization_method
'Crystallization was conducted by slow diffusion in hexane/ethyl acetate'
_exptl_crystal_size_max          0.418
_exptl_crystal_size_mid          0.224
_exptl_crystal_size_min          0.136
_refine_diff_density_max         0.468
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     248
_refine_ls_number_reflns         4592
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0240
_refine_ls_R_factor_gt           0.0203
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0225P)^2^+1.2471P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0491
_refine_ls_wR_factor_ref         0.0503
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4139
_reflns_number_total             4592
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12123_si_005.cif
_cod_data_source_block           cm92zsa
_cod_database_code               4133643
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.584
_shelx_estimated_absorpt_t_min   0.259
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C7(H7), C12(H12), C11(H11), C8(H8)
3.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
3.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C5(H5), C2(H2)
3.d Disordered Me refined as rotating group:
 C16(H16A,H16B,H16C,H16D,H16E,H16F)
3.e Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
3.f Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              11432
_shelx_hkl_checksum              53018
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on the spindle axis of 4 1 3.'
_olex2_submission_original_sample_id halohydrin
_olex2_submission_special_instructions 'No special instructions were received'