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_1573797
_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_absolute_configuration ad
_chemical_formula_moiety         'C18 H16 Cl N O2'
_chemical_formula_sum            'C18 H16 Cl N O2'
_chemical_formula_weight         313.76
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-31
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-12-10 deposited with the CCDC.	2025-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.761(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.74490(10)
_cell_length_b                   12.6197(3)
_cell_length_c                   12.8104(2)
_cell_measurement_reflns_used    7835
_cell_measurement_temperature    301.46(10)
_cell_measurement_theta_max      77.0390
_cell_measurement_theta_min      3.4250
_cell_volume                     1574.65(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      301.46(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.930
_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     74.00 102.00   0.50    0.15    --   47.57 133.00 116.00   56
  2  \w     72.00 120.00   0.50    0.15    --   47.57 135.00 -64.00   96
  3  \w    141.00 166.00   0.50    0.61    --  107.75 135.00 -64.00   50
  4  \w     95.00 131.00   0.50    0.61    --  107.75  19.00 120.00   72
  5  \w    146.00 175.00   0.50    0.61    --  107.75  19.00 120.00   58
  6  \w     58.00 108.00   0.50    0.61    --  107.75-109.00  72.38  100
  7  \w     33.00  60.00   0.50    0.15    --   47.57-133.00  48.00   54
  8  \w     35.00 118.00   0.50    0.61    --  107.75-133.00  48.00  166
  9  \w     35.00  63.00   0.50    0.61    --  107.75-135.00-129.00   56
 10  \w     49.00  80.00   0.50    0.61    --  107.75 -77.00-150.00   62
 11  \w     36.00  62.00   0.50    0.61    --  107.75 -57.00-180.00   52
 12  \w     -3.00  23.00   0.50    0.15    --   47.57 -19.00 -90.00   52
 13  \w    -27.00  23.00   0.50    0.15    --   47.57 -19.00  30.00  100
 14  \w     36.00  61.00   0.50    0.61    --  107.75 -57.00  90.00   50
 15  \w     36.00  63.00   0.50    0.61    --  107.75 -57.00  30.00   54
 16  \w    -26.00  28.00   0.50    0.15    --  -47.57  19.00  30.00  108
 17  \w    -98.00 -51.00   0.50    0.15    --  -47.57 133.00 116.00   94
 18  \w   -115.00 -71.00   0.50    0.61    -- -100.00 133.00 116.00   88
 19  \w   -111.00 -28.00   0.50    0.61    -- -100.00 125.00 -90.00  166
 20  \w    -56.00 -28.00   0.50    0.61    -- -100.00  57.00-150.00   56
 21  \w   -172.00-147.00   0.50    0.61    -- -100.00 -37.00 -60.00   50
 22  \w   -161.00-136.00   0.50    0.61    -- -100.00 -99.00  90.00   50
 23  \w   -119.00 -91.00   0.50    0.61    -- -100.00 -99.00  90.00   56
 24  \w   -149.00-124.00   0.50    0.61    -- -100.00-133.00  48.00   50
 25  \w   -173.00 -91.00   0.50    0.61    -- -100.00 -99.00 -30.00  164
 26  \w   -127.00 -87.00   0.50    0.61    -- -100.00 -37.00 -60.00   80
 27  \w   -103.00 -77.00   0.50    0.61    -- -100.00-135.00-129.00   52
 28  \w     69.00  94.00   0.50    0.15    --   47.57  77.00 -90.00   50
 29  \w     35.00  60.00   0.50    0.61    --  107.75 -57.00 -60.00   50
 30  \w     35.00  60.00   0.50    0.61    --  107.75 -57.00 120.00   50
 31  \w     35.00  60.00   0.50    0.61    --  107.75 -57.00-120.00   50
;
_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      0.0338799000
_diffrn_orient_matrix_UB_12      -0.0337317000
_diffrn_orient_matrix_UB_13      -0.1119216000
_diffrn_orient_matrix_UB_21      -0.0044810000
_diffrn_orient_matrix_UB_22      -0.1172606000
_diffrn_orient_matrix_UB_23      0.0331240000
_diffrn_orient_matrix_UB_31      -0.1543929000
_diffrn_orient_matrix_UB_32      -0.0040112000
_diffrn_orient_matrix_UB_33      -0.0292665000
_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  0.0502
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11508
_diffrn_reflns_point_group_measured_fraction_full 0.877
_diffrn_reflns_point_group_measured_fraction_max 0.811
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.922
_diffrn_reflns_theta_min         3.452
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.197
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86042
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             656
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1729 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.268(10)
_refine_ls_extinction_coef       0.0051(8)
_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   1.097
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     410
_refine_ls_number_reflns         5451
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0449
_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^)+(0.0625P)^2^+0.2953P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1198
_refine_ls_wR_factor_ref         0.1306
_reflns_Friedel_coverage         0.666
_reflns_Friedel_fraction_full    0.758
_reflns_Friedel_fraction_max     0.680
_reflns_number_gt                4909
_reflns_number_total             5451
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06597b3.cif
_cod_data_source_block           huyuehong_0831_auto
_cod_depositor_comments
;
Adding full bibliography for 1573796--1573800.cif.

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C36 H32 Cl2 N2 O4'
_cod_original_formula_weight         627.53
_cod_original_formula_moiety         '2(C18 H16 Cl N O2)'
_cod_original_formula_units_Z            2
_cod_database_code               1573797
_shelx_shelxl_version_number     2018/3
_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:
 C6(H6), C14(H14)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C11(H11), C15(H15), C28(H28), C29(H29), C30(H30), C32(H32),
 C9(H9), C13(H13), C25(H25), C26(H26), C31(H31), C33(H33), C34(H34), C35(H35)
2.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C17(H17A,H17B,H17C), C23(H23A,H23B,H23C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              83510
_shelx_hkl_checksum              51805
_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 3.882
_oxdiff_exptl_absorpt_empirical_full_min 0.239