Asymmetric Aza-Wacker-Type Cyclization of N-Ts Hydrazine-Tethered Tetrasubstituted Olefins: Synthesis of Pyrazolines Bearing One Quaternary or Two Vicinal Stereocenters.
Kou, Xuezhen; Shao, Qihang; Ye, Chenghao; Yang, Guoqiang; Zhang, Wanbin; Journal of the American Chemical Society 140 (2018) 7587–7597; doi:10.1021/jacs.8b02865

data_4132291
_publ_section_title
;
 Asymmetric Aza-Wacker-Type Cyclization of N-Ts Hydrazine-Tethered
 Tetrasubstituted Olefins: Synthesis of Pyrazolines Bearing One Quaternary
 or Two Vicinal Stereocenters.
;
_journal_issue                   24
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              7587
_journal_page_last               7597
_journal_paper_doi               10.1021/jacs.8b02865
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H24 N2 O2 S'
_chemical_formula_sum            'C24 H24 N2 O2 S'
_chemical_formula_weight         404.51
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.557(4)
_cell_length_b                   12.498(4)
_cell_length_c                   14.777(4)
_cell_measurement_reflns_used    9469
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.30
_cell_measurement_theta_min      3.54
_cell_volume                     2134.4(12)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker D8 VENTURE CMOS photon 100'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12902
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.347
_diffrn_reflns_theta_min         4.858
_exptl_absorpt_coefficient_mu    1.518
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6231
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.259
_exptl_crystal_description       block
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.220
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 1452 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.038(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         3831
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0344
_refine_ls_R_factor_gt           0.0321
_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^)+(0.0575P)^2^+0.1982P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.0914
_reflns_Friedel_coverage         0.737
_reflns_Friedel_fraction_full    0.969
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                3604
_reflns_number_total             3831
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b02865_si_003.cif
_cod_data_source_block           t_a
_cod_original_cell_volume        2134.3(11)
_cod_database_code               4132291
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.659
_shelx_estimated_absorpt_t_max   0.731
_shelx_res_checksum              66177
_shelx_hkl_checksum              43792