Diastereodivergent and Enantioselective Access to Spiroepoxides via Organocatalytic Epoxidation of Unsaturated Pyrazolones.
Meninno, Sara; Roselli, Angelo; Capobianco, Amedeo; Overgaard, Jacob; Lattanzi, Alessandra; Organic letters 19 (2017) 5030–5033; doi:10.1021/acs.orglett.7b02189

data_1547176
_publ_section_title
;
 Diastereodivergent and Enantioselective Access to Spiroepoxides via
 Organocatalytic Epoxidation of Unsaturated Pyrazolones.
;
_journal_issue                   19
_journal_name_full               'Organic letters'
_journal_page_first              5030
_journal_page_last               5033
_journal_paper_doi               10.1021/acs.orglett.7b02189
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H13 Br N2 O2'
_chemical_formula_sum            'C17 H13 Br N2 O2'
_chemical_formula_weight         357.20
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_symmetry_space_group_name_Hall  'P 4cw'
_symmetry_space_group_name_H-M   'P 43'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.4914(3)
_cell_length_b                   14.4914(3)
_cell_length_c                   14.4935(5)
_cell_measurement_reflns_used    4894
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.3540
_cell_measurement_theta_min      1.9630
_cell_volume                     3043.64(14)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -11.00  68.00   1.00   22.50    --   18.69 -99.00-180.00   79
  2  \w    -15.00  68.00   1.00   22.50    --   18.69  19.00  30.00   83
  3  \w   -121.00 -41.00   1.00   22.50    --  -19.78-178.00-120.00   80
  4  \w   -112.00  22.00   1.00   22.50    --  -19.78 -57.00  90.00  134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0222158000
_diffrn_orient_matrix_UB_12      -0.0362025000
_diffrn_orient_matrix_UB_13      -0.0242053000
_diffrn_orient_matrix_UB_21      0.0207131000
_diffrn_orient_matrix_UB_22      0.0327067000
_diffrn_orient_matrix_UB_23      -0.0299742000
_diffrn_orient_matrix_UB_31      0.0383980000
_diffrn_orient_matrix_UB_32      0.0034585000
_diffrn_orient_matrix_UB_33      0.0302161000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1103
_diffrn_reflns_av_unetI/netI     0.2080
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            19151
_diffrn_reflns_point_group_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.019
_diffrn_reflns_theta_min         1.987
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.709
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.768
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
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    1.559
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1440
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.151
_exptl_crystal_size_min          0.103
_refine_diff_density_max         0.821
_refine_diff_density_min         -0.521
_refine_diff_density_rms         0.091
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.029(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.669
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         5623
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.669
_refine_ls_R_factor_all          0.0841
_refine_ls_R_factor_gt           0.0553
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.1055
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    0.887
_reflns_Friedel_fraction_max     0.886
_reflns_number_gt                3296
_reflns_number_total             5623
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02189_si_002.cif
_cod_data_source_block           exp_286
_cod_depositor_comments
'Adding full bibliography for 1547176--1547177.cif.'
_cod_original_cell_volume        3043.63(18)
_cod_database_code               1547176
_chemical_oxdiff_formula         'C17 H13 Br N2 O2'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00D(H00E), C00N(H00N)
2.b Aromatic/amide H refined with riding coordinates:
 C00C(H00D), C00F(H00F), C00I(H00I), C00L(H00L), C00M(H00M), C00T(H00T),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C010(H010), C011(H011), C012(H012),
 C013(H013), C014(H014), C015(H015), C016(H016), C017(H017), C018(H018)
2.c Idealised Me refined as rotating group:
 C00E(H00G,H00H,H00J), C00V(H00A,H00B,H00C)
;
_shelx_res_checksum              72075
_shelx_hkl_checksum              23946
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-03-11
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.730
_oxdiff_exptl_absorpt_empirical_full_min 0.587