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_4133644
_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 H19 N3 O6'
_chemical_formula_sum            'C17 H19 N3 O6'
_chemical_formula_weight         361.35
_chemical_name_systematic        diol
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3 :H'
_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                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   36.4159(9)
_cell_length_b                   36.4159(9)
_cell_length_c                   6.6637(2)
_cell_measurement_reflns_used    33823
_cell_volume                     7652.9(4)
_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      100.03
_diffrn_detector                 'Bruker Photon 100 area detector'
_diffrn_detector_type            'photon counter area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture/Photon 100'
_diffrn_measurement_method       'profile data from \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  0.0292
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            35277
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.329
_diffrn_reflns_theta_min         2.427
_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    0.913
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5982
_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    1.411
_exptl_crystal_description       prism
_exptl_crystal_F_000             3420
_exptl_crystal_recrystallization_method
'Crystalization of racemic mixtures was conducted by slow diffusion in hexanes/ethyl acetate co-solvent.'
_exptl_crystal_size_max          0.823
_exptl_crystal_size_mid          0.292
_exptl_crystal_size_min          0.226
_refine_diff_density_max         0.173
_refine_diff_density_min         -0.202
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.29(13)
_refine_ls_extinction_coef       0.00114(5)
_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   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     480
_refine_ls_number_reflns         6229
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0261
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0389P)^2^+4.3410P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0668
_refine_ls_wR_factor_ref         0.0672
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                6161
_reflns_number_total             6229
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12123_si_003.cif
_cod_data_source_block           146
_cod_original_sg_symbol_H-M      'R 3'
_cod_database_code               4133644
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.820
_shelx_estimated_absorpt_t_min   0.520
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.71(13)
 0.29(13)
2. 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
3. Others
 Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C8(H8), C11(H11), C12(H12), C25(H25), C28(H28), C29(H29)
4.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C32(H32A,H32B)
4.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C5(H5), C9(H9A), C10(H10A), C2(H2), C18(H18), C19(H19), C22(H22),
 C26(H26), C27(H27)
4.d Disordered Me refined as rotating group:
 C33(H33A,H33B,H33C,H33D,H33E,H33F)
4.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C34(H34A,H34B,H34C)
4.f Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4), O9(H9), O10(H10)
;
_shelx_res_checksum              41737
_shelx_hkl_checksum              97560
_olex2_exptl_crystal_mounting_method
'the crystal was mounted on a loop with spindle axis of 5 -6 1.'
_olex2_submission_original_sample_id diol
_olex2_submission_special_instructions 'No special instructions were received'