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_1573798
_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 unk
_chemical_formula_moiety         'C21 H19 F2 N O2'
_chemical_formula_sum            'C21 H19 F2 N O2'
_chemical_formula_weight         355.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'I -2ya'
_space_group_name_H-M_alt        'I 1 a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-26
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2024-12-10 deposited with the CCDC.	2025-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.850(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7705(2)
_cell_length_b                   13.1781(3)
_cell_length_c                   14.4870(4)
_cell_measurement_reflns_used    8309
_cell_measurement_temperature    271.8(9)
_cell_measurement_theta_max      76.7210
_cell_measurement_theta_min      4.5580
_cell_volume                     1811.07(8)
_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 (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      271.8(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.967
_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     65.00 102.00   0.50    0.05    --   44.44 147.00  85.00   74
  2  \w     62.00 168.00   0.50    0.29    --  112.00 147.00  85.00  212
  3  \w    102.00 127.00   0.50    0.29    --  112.00 124.00 -79.00   50
  4  \w    127.00 152.00   0.50    0.29    --  112.00  61.00-150.00   50
  5  \w     97.00 122.00   0.50    0.29    --  112.00  61.00-150.00   50
  6  \w     44.00  92.00   0.50    0.29    --  112.00 -94.00-120.00   96
  7  \w     50.00  75.00   0.50    0.29    --  112.00-124.00-159.00   50
  8  \w     82.00 107.00   0.50    0.29    --  112.00-125.00 -60.00   50
  9  \w     51.00  77.00   0.50    0.29    --  112.00-125.00 -60.00   52
 10  \w     59.00  84.00   0.50    0.29    --  112.00-147.00  35.00   50
 11  \w     40.00 111.00   0.50    0.29    --  112.00-125.00 150.00  142
 12  \w    -25.00  22.00   0.50    0.05    --   44.44 -19.00   0.00   94
 13  \w    -33.00  12.00   0.50    0.05    --   44.44 -19.00 -60.00   90
 14  \w     58.00 102.00   0.50    0.29    --  112.00 -77.00-180.00   88
 15  \w     56.00  82.00   0.50    0.29    --  112.00 -77.00   0.00   52
 16  \w     39.00  67.00   0.50    0.29    --  112.00 -61.00  30.00   56
 17  \w   -173.00-118.00   0.50    0.29    -- -100.00 -45.00-150.00  110
 18  \w   -136.00 -90.00   0.50    0.29    -- -100.00-147.00  35.00   92
 19  \w   -118.00 -67.00   0.50    0.05    --  -44.44-147.00  35.00  102
 20  \w   -173.00 -90.00   0.50    0.29    -- -100.00 -61.00 -60.00  166
 21  \w    -28.00  25.00   0.50    0.05    --  -44.44  19.00-120.00  106
 22  \w    -53.00 -28.00   0.50    0.29    -- -100.00  45.00  60.00   50
 23  \w    -54.00 -27.00   0.50    0.29    -- -100.00  45.00  90.00   54
 24  \w    -53.00 -27.00   0.50    0.29    -- -100.00  45.00 150.00   52
 25  \w    -95.00 -70.00   0.50    0.05    --  -44.44 147.00  85.00   50
 26  \w   -127.00 -81.00   0.50    0.29    -- -100.00 147.00  85.00   92
 27  \w    -92.00 -67.00   0.50    0.29    -- -100.00 124.00 -79.00   50
 28  \w    -96.00 -46.00   0.50    0.05    --  -44.44 124.00 -79.00  100
 29  \w     74.00 110.00   0.50    0.05    --  112.00-124.00-159.00   72
 30  \w    -44.00 -11.00   0.50    0.05    --  -44.32  37.00-180.00   66
 31  \w      0.00  26.00   0.50    0.05    --  -44.32  37.00-180.00   52
 32  \w    -32.00  10.00   0.50    0.05    --   44.32 -19.00-150.00   84
 33  \w     42.00 123.00   0.50    0.05    --   44.32  19.00  30.00  162
 34  \w      3.00  39.00   0.50    0.05    --   44.32 -37.00 -30.00   72
 35  \w   -103.00 -72.00   0.50    0.05    -- -100.00 125.00  90.00   62
 36  \w   -129.00 -88.00   0.50    0.05    -- -100.00 -61.00 120.00   82
 37  \w    -73.00 -37.00   0.50    0.05    -- -100.00 125.00-120.00   72
 38  \w   -110.00 -85.00   0.50    0.05    -- -100.00 124.00 -79.00   50
 39  \w   -108.00 -60.00   0.50    0.05    -- -100.00 125.00  30.00   96
 40  \w    -53.00 -27.00   0.50    0.05    -- -100.00  45.00-120.00   52
 41  \w    -57.00 -29.00   0.50    0.05    -- -100.00 125.00  30.00   56
 42  \w   -108.00 -78.00   0.50    0.05    -- -100.00  77.00  90.00   60
 43  \w    -52.00 -26.00   0.50    0.05    -- -100.00 125.00  90.00   52
 44  \w   -173.00-134.00   0.50    0.05    -- -100.00 -61.00 120.00   78
 45  \w    -60.00 -34.00   0.50    0.05    -- -100.00  77.00 -90.00   52
 46  \w   -158.00 -81.00   0.50    0.05    -- -100.00 -30.00  30.00  154
 47  \w   -106.00 -80.00   0.50    0.05    -- -100.00  77.00 -90.00   52
 48  \w    -64.00 -38.00   0.50    0.05    -- -100.00 124.00 -79.00   52
 49  \w    -52.00 -26.00   0.50    0.05    -- -100.00  45.00-150.00   52
 50  \w   -163.00 -83.00   0.50    0.05    -- -100.00-125.00-180.00  160
 51  \w    -67.00 -41.00   0.50    0.05    -- -100.00  77.00  90.00   52
 52  \w     39.00  64.00   0.50    0.05    --  112.00 -61.00 -60.00   50
 53  \w     81.00 106.00   0.50    0.05    --  112.00-125.00  90.00   50
 54  \w     39.00  64.00   0.50    0.05    --  112.00 -61.00-180.00   50
 55  \w     42.00  67.00   0.50    0.05    --  112.00-125.00  90.00   50
 56  \w     39.00  64.00   0.50    0.05    --  112.00 -61.00   0.00   50
 57  \w     66.00  91.00   0.50    0.05    --  112.00 -94.00-150.00   50
 58  \w    142.00 171.00   0.50    0.05    --  112.00  15.00  30.00   58
 59  \w     83.00 109.00   0.50    0.05    --  112.00  15.00  30.00   52
 60  \w     87.00 112.00   0.50    0.05    --  112.00-125.00  30.00   50
 61  \w    149.00 175.00   0.50    0.05    --  112.00  61.00   0.00   52
 62  \w   -117.00 -92.00   0.50    0.05    --  -44.32-147.00  35.00   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      -0.0415636000
_diffrn_orient_matrix_UB_12      -0.0602157000
_diffrn_orient_matrix_UB_13      -0.0936833000
_diffrn_orient_matrix_UB_21      0.0381578000
_diffrn_orient_matrix_UB_22      -0.0998134000
_diffrn_orient_matrix_UB_23      0.0555516000
_diffrn_orient_matrix_UB_31      -0.1522878000
_diffrn_orient_matrix_UB_32      -0.0085889000
_diffrn_orient_matrix_UB_33      0.0115641000
_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  0.0321
_diffrn_reflns_av_unetI/netI     0.0193
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            12116
_diffrn_reflns_point_group_measured_fraction_full 0.755
_diffrn_reflns_point_group_measured_fraction_max 0.716
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.561
_diffrn_reflns_theta_min         4.598
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.812
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95679
_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    1.303
_exptl_crystal_description       needle
_exptl_crystal_F_000             744
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.133
_refine_diff_density_min         -0.165
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 699 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         2762
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0372
_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^)+(0.0720P)^2^+0.0594P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1082
_reflns_Friedel_coverage         0.476
_reflns_Friedel_fraction_full    0.510
_reflns_Friedel_fraction_max     0.463
_reflns_number_gt                2484
_reflns_number_total             2762
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc06597b3.cif
_cod_data_source_block           huyuehong1-zhfm_0426_auto
_cod_depositor_comments
'Adding full bibliography for 1573796--1573800.cif.'
_cod_original_cell_volume        1811.06(8)
_cod_database_code               1573798
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(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:
 N1(H1), C7(H7), C8(H8), C10(H10), C11(H11), C13(H13), C17(H17), C19(H19),
 C20(H20)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              10038
_shelx_hkl_checksum              4686
_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 2.709
_oxdiff_exptl_absorpt_empirical_full_min 0.400