One-pot Nazarov cyclization/oxidative 1,2-carbon rearrangement/Ritter reaction to access 5-quaternary-4-amidocyclopent-2-enones and 2-quaternary-3-amidoindanones.
Hu, Yue-Hong; Chen, Yu-Ting; He, Zhi-Juan; Gan, Zhang-Yan; Zhang, Ling-Hui; Xi, Wen-Jie; Li, Baosheng; Zhang, Fu-Min; Chemical communications (Cambridge, England) 61 (2025) 3720–3723; doi:10.1039/d4cc06597b

data_1573800
_publ_section_title
;
 One-pot Nazarov cyclization/oxidative 1,2-carbon rearrangement/Ritter
 reaction to access 5-quaternary-4-amidocyclopent-2-enones and
 2-quaternary-3-amidoindanones.
;
_journal_issue                   18
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3720
_journal_page_last               3723
_journal_paper_doi               10.1039/d4cc06597b
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C21 H19 Br2 N O2'
_chemical_formula_sum            'C21 H19 Br2 N O2'
_chemical_formula_weight         477.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-13 deposited with the CCDC.	2025-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.0437(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.9874(2)
_cell_length_b                   9.81932(13)
_cell_length_c                   24.6758(3)
_cell_measurement_reflns_used    10373
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      75.8830
_cell_measurement_theta_min      3.7870
_cell_volume                     3890.77(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.945
_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    -54.00 -25.00   0.50    0.05    -- -100.00  45.00 120.00   58
  2  \w    -52.00 -25.00   0.50    0.05    -- -100.00  45.00  60.00   54
  3  \w    -54.00 -29.00   0.50    0.05    -- -100.00  45.00   0.00   50
  4  \w    -50.00 -25.00   0.50    0.05    -- -100.00  45.00  30.00   50
  5  \w    -54.00 -25.00   0.50    0.05    -- -100.00  45.00 -30.00   58
  6  \w    -74.00 -32.00   0.50    0.05    -- -100.00  61.00-120.00   84
  7  \w    -44.00  27.00   0.50    0.05    --  -44.63  37.00 120.00  142
  8  \w    -33.00  23.00   0.50    0.05    --   44.63 -19.00 -30.00  112
  9  \w    -31.00  39.00   0.50    0.05    --   44.63 -37.00-120.00  140
 10  \w     43.00  68.00   0.50    0.05    --  108.93 -61.00-150.00   50
 11  \w     69.00 107.00   0.50    0.05    --   44.63 145.00  39.00   76
 12  \w     83.00 131.00   0.50    0.05    --  108.93 126.00-128.00   96
 13  \w    135.00 169.00   0.50    0.05    --  108.93 126.00-128.00   68
 14  \w    144.00 175.00   0.50    0.05    --  108.93  61.00-150.00   62
 15  \w     92.00 129.00   0.50    0.05    --  108.93  61.00-150.00   74
 16  \w     96.00 160.00   0.50    0.05    --  108.93  45.00  30.00  128
 17  \w     37.00  64.00   0.50    0.05    --  108.93 -94.00 150.00   54
 18  \w     50.00  75.00   0.50    0.05    --  108.93-126.00 153.00   50
 19  \w     56.00 125.00   0.50    0.05    --  108.93-145.00 -13.00  138
 20  \w     70.00 101.00   0.50    0.05    --  108.93 -94.00 -60.00   62
 21  \w    -71.00 -46.00   0.50    0.05    --  -44.63 145.00  39.00   50
 22  \w    -92.00 -66.00   0.50    0.05    -- -100.00 137.00 116.16   52
 23  \w   -120.00 -95.00   0.50    0.05    -- -100.00 137.00 116.16   50
 24  \w   -112.00 -65.00   0.50    0.05    -- -100.00 125.00 150.00   94
 25  \w    -65.00 -39.00   0.50    0.05    -- -100.00 125.00 120.00   52
 26  \w   -110.00 -76.00   0.50    0.05    -- -100.00 125.00 120.00   68
 27  \w   -105.00 -79.00   0.50    0.05    -- -100.00 145.00  39.00   52
 28  \w    -95.00 -59.00   0.50    0.05    --  -44.63 126.00-128.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0037191000
_diffrn_orient_matrix_UB_12      -0.1526496000
_diffrn_orient_matrix_UB_13      -0.0150533000
_diffrn_orient_matrix_UB_21      0.0428617000
_diffrn_orient_matrix_UB_22      -0.0346228000
_diffrn_orient_matrix_UB_23      0.0637604000
_diffrn_orient_matrix_UB_31      -0.0857509000
_diffrn_orient_matrix_UB_32      -0.0106764000
_diffrn_orient_matrix_UB_33      0.0084070000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0367
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            12974
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.096
_diffrn_reflns_theta_min         3.790
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.404
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42775
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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    1.629
_exptl_crystal_description       block
_exptl_crystal_F_000             1904
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.775
_refine_diff_density_min         -1.181
_refine_diff_density_rms         0.085
_refine_ls_extinction_coef       0.00024(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     243
_refine_ls_number_reflns         3856
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0394
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0525P)^2^+12.0932P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1026
_refine_ls_wR_factor_ref         0.1044
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3623
_reflns_number_total             3856
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06597b3.cif
_cod_data_source_block           huyh_1211_auto
_cod_depositor_comments
'Adding full bibliography for 1573796--1573800.cif.'
_cod_original_cell_volume        3890.75(10)
_cod_database_code               1573800
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.813
_shelx_estimated_absorpt_t_min   0.345
_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:
 C2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C11(H11), C15(H15), C16(H16), C18(H18), C19(H19)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              72890
_shelx_hkl_checksum              52468
_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 3.113
_oxdiff_exptl_absorpt_empirical_full_min 0.394