Quaternary Carbon Center Forming Formal [3 + 3] Cycloaddition Reaction via Bifunctional Catalysis: Asymmetric Synthesis of Spirocyclohexene Pyrazolones.
Liu, Jin-Yu; Zhao, Jing; Zhang, Jia-Lu; Xu, Peng-Fei; Organic letters 19 (2017) 1846–1849; doi:10.1021/acs.orglett.7b00610

data_1545957
_publ_section_title
;
 Quaternary Carbon Center Forming Formal [3 + 3] Cycloaddition Reaction
 via Bifunctional Catalysis: Asymmetric Synthesis of Spirocyclohexene
 Pyrazolones.
;
_journal_issue                   7
_journal_name_full               'Organic letters'
_journal_page_first              1846
_journal_page_last               1849
_journal_paper_doi               10.1021/acs.orglett.7b00610
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H24 Br N3 O3'
_chemical_formula_sum            'C32 H24 Br N3 O3'
_chemical_formula_weight         578.45
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-12-14
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.6027(3)
_cell_length_b                   16.7807(6)
_cell_length_c                   21.1178(5)
_cell_measurement_reflns_used    1520
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      26.0570
_cell_measurement_theta_min      4.0440
_cell_volume                     2694.18(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9953
_diffrn_measured_fraction_theta_max 0.7623
_diffrn_measurement_details
;
  1 omega  -11.00   37.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -57.0000 -150.0000 48

  2 omega  -29.00   68.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867   19.0000   30.0000 97
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0048578000
_diffrn_orient_matrix_UB_12      0.0418445000
_diffrn_orient_matrix_UB_13      0.0044380000
_diffrn_orient_matrix_UB_21      0.0860486000
_diffrn_orient_matrix_UB_22      -0.0041633000
_diffrn_orient_matrix_UB_23      0.0125308000
_diffrn_orient_matrix_UB_31      0.0356628000
_diffrn_orient_matrix_UB_32      0.0043140000
_diffrn_orient_matrix_UB_33      -0.0308516000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0848
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            6660
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.52
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.565
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86427
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.424
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.010(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         4624
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0457
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0138P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0775
_refine_ls_wR_factor_ref         0.0857
_reflns_number_gt                3777
_reflns_number_total             4624
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b00610_si_002.cif
_cod_data_source_block           liujy_1213_2
_cod_database_code               1545957
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25), C26(H26), C28(H28),
  C29(H29), C30(H30), C31(H31), C32(H32)
;
_olex2_date_sample_data_collection 2016-12-14
_olex2_submission_special_instructions 'No special instructions were received'