Enantioselective annulations for dihydroquinolones by in situ generation of azolium enolates.
Lee, Anna; Younai, Ashkaan; Price, Christopher K.; Izquierdo, Javier; Mishra, Rama K.; Scheidt, Karl A.; Journal of the American Chemical Society 136 (2014) 10589–10592; doi:10.1021/ja505880r

data_4122263
_publ_section_title
;
 Enantioselective annulations for dihydroquinolones by in situ generation
 of azolium enolates.
;
_journal_issue                   30
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10589
_journal_page_last               10592
_journal_paper_doi               10.1021/ja505880r
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H22 Br N O3'
_chemical_formula_sum            'C21 H22 Br N O3'
_chemical_formula_weight         416.30
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-04-18
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.5638(2)
_cell_length_b                   13.0804(3)
_cell_length_c                   19.4333(4)
_cell_measurement_reflns_used    9861
_cell_measurement_temperature    99.96
_cell_measurement_theta_max      65.05
_cell_measurement_theta_min      4.55
_cell_volume                     1922.68(8)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      99.96
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22256
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        65.042
_diffrn_reflns_theta_max         65.042
_diffrn_reflns_theta_min         4.074
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.076
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6594
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0653 before and 0.0549 after correction. The Ratio of minimum to maximum transmission is 0.8762. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       needles
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.261
_refine_diff_density_min         -0.153
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1297 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.013(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         3260
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0217
_refine_ls_R_factor_gt           0.0197
_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^)+(0.0242P)^2^+0.3586P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0460
_refine_ls_wR_factor_ref         0.0469
_reflns_Friedel_coverage         0.725
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3109
_reflns_number_total             3260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja505880r_si_002.cif
_cod_data_source_block           cu_al_08_20_0m
_cod_depositor_comments          'Adding full bibliography for 4122263.cif.'
_cod_database_code               4122263
_shelxl_version_number           2012-9
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.573
_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:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C17(H17), C19(H19), C20(H20), C21(H21)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              94397
_shelx_hkl_checksum              98348