Copper-Assisted Direct Nitration of Cyclic Ketones with Ceric Ammonium Nitrate for the Synthesis of Tertiary α-Nitro-α-substituted Scaffolds.
Zhang, Zhi-Qiang; Chen, Tao; Zhang, Fu-Min; Organic letters 19 (2017) 1124–1127; doi:10.1021/acs.orglett.7b00040

data_1545437
_publ_section_title
;
 Copper-Assisted Direct Nitration of Cyclic Ketones with Ceric Ammonium
 Nitrate for the Synthesis of Tertiary \a-Nitro-\a-substituted Scaffolds.
;
_journal_issue                   5
_journal_name_full               'Organic letters'
_journal_page_first              1124
_journal_page_last               1127
_journal_paper_doi               10.1021/acs.orglett.7b00040
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C12 H12 Br N O3'
_chemical_formula_sum            'C12 H12 Br N O3'
_chemical_formula_weight         298.14
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-11-04
_audit_creation_method
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Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   7.7792(10)
_cell_length_b                   11.9136(13)
_cell_length_c                   25.989(3)
_cell_measurement_reflns_used    1153
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.5010
_cell_measurement_theta_min      3.8890
_cell_volume                     2408.6(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -18.00   19.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3492  -99.0000 -150.0000 37

  2 omega   36.00   62.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305  178.0000  120.0000 26

  3 omega   53.00   93.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305   57.0000 -120.0000 40

  4 omega   32.00   82.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305   57.0000 -150.0000 50

  5 omega    2.00   72.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6305   38.0000  150.0000 70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0912360000
_diffrn_orient_matrix_UB_12      0.0002641000
_diffrn_orient_matrix_UB_13      0.0001480000
_diffrn_orient_matrix_UB_21      0.0006585000
_diffrn_orient_matrix_UB_22      -0.0338459000
_diffrn_orient_matrix_UB_23      -0.0225198000
_diffrn_orient_matrix_UB_31      -0.0001886000
_diffrn_orient_matrix_UB_32      0.0489494000
_diffrn_orient_matrix_UB_33      -0.0154080000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1885
_diffrn_reflns_av_unetI/netI     0.1724
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            7804
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.42
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.409
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37557
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
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    1.644
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.966
_refine_diff_density_min         -0.980
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.974
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     154
_refine_ls_number_reflns         2377
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.974
_refine_ls_R_factor_all          0.1852
_refine_ls_R_factor_gt           0.1015
_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^)+(0.1618P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2430
_refine_ls_wR_factor_ref         0.3221
_reflns_number_gt                1093
_reflns_number_total             2377
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b00040_si_002.cif
_cod_data_source_block           zhangfm_1102
_cod_database_code               1545437
_reflns_odcompleteness_completeness 99.54
_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 Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12)
;
_olex2_date_sample_data_collection 2016-11-02
_olex2_submission_special_instructions 'No special instructions were received'