Rearrangement-driven divergent synthesis: a metal-free tandem annulation for CF3-functionalized 1-(aminomethyl)naphthalen-2-ols and 1-(2-naphthyl)azetidines
Wang, Bin; Li, Zekun; Cao, Hua; Green Chemistry 27 (2025) 15074–15080; doi:10.1039/D5GC05046D

data_7251256
_publ_section_title
;
 Rearrangement-driven divergent synthesis: a metal-free tandem annulation
 for CF3-functionalized 1-(aminomethyl)naphthalen-2-ols and
 1-(2-naphthyl)azetidines
;
_journal_issue                   47
_journal_name_full               'Green Chemistry'
_journal_page_first              15074
_journal_page_last               15080
_journal_paper_doi               10.1039/D5GC05046D
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C15 H14 F3 N O2'
_chemical_formula_sum            'C15 H14 F3 N O2'
_chemical_formula_weight         297.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2025-03-31
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-05-16 deposited with the CCDC.	2025-11-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.345(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   5.49673(14)
_cell_length_b                   20.9321(5)
_cell_length_c                   23.4394(5)
_cell_measurement_reflns_used    13510
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      72.6330
_cell_measurement_theta_min      4.2070
_cell_volume                     2694.63(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.121a 64-bit (release 24-04-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.952
_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     36.00  78.00   0.50    0.05    --   61.98-126.00 -90.00   84
  2  \w     24.00  75.00   0.50    0.05    --   61.98-126.00-120.00  102
  3  \w     62.00  88.00   0.50    0.05    --   71.30-126.00 -90.00   52
  4  \w     24.00  49.00   0.50    0.05    --   61.98-126.00 -60.00   50
  5  \w     24.00  77.00   0.50    0.05    --   61.98-126.00 -30.00  106
  6  \w     61.00  91.00   0.50    0.05    --   74.09-126.00 -30.00   60
  7  \w     36.00  89.00   0.50    0.05    --   74.09-126.00   0.00  106
  8  \w     36.00  91.00   0.50    0.05    --   74.09-126.00 -60.00  110
  9  \w     59.00  85.00   0.50    0.05    --   71.30-126.00 -60.00   52
 10  \w     43.00  69.00   0.50    0.05    --   74.09-126.00 -90.00   52
 11  \w     54.00  91.00   0.50    0.05    --   74.09-126.00-120.00   74
 12  \w     35.00  60.00   0.50    0.05    --   71.30-120.00-172.00   50
 13  \w     38.00  64.00   0.50    0.05    --   74.09-120.00-172.00   52
 14  \w     25.00  69.00   0.50    0.05    --   61.98-120.00-172.00   88
 15  \w     37.00  91.00   0.50    0.05    --   74.09-126.00-150.00  108
 16  \w     62.00  87.00   0.50    0.05    --   75.65-118.00 -49.86   50
 17  \w     68.00 108.00   0.50    0.05    --   74.09  15.00 -90.00   80
 18  \w     57.00  93.00   0.50    0.05    --   61.98  15.00-180.00   72
 19  \w     57.00  91.00   0.50    0.05    --   61.98  15.00 -90.00   68
 20  \w     62.00  92.00   0.50    0.05    --   61.98  15.00-120.00   60
 21  \w     71.00  99.00   0.50    0.05    --   61.98  15.00 -60.00   56
 22  \w     72.00 101.00   0.50    0.05    --   74.09  15.00-120.00   58
 23  \w     81.00 108.00   0.50    0.05    --   74.09  15.00-180.00   54
 24  \w     54.00  79.00   0.50    0.05    --   61.98  15.00 -30.00   50
 25  \w     55.00  95.00   0.50    0.05    --   61.98  15.00   0.00   80
 26  \w     73.00 113.00   0.50    0.05    --   74.09  15.00 -30.00   80
 27  \w     54.00 100.00   0.50    0.05    --   61.98  15.00 120.00   92
 28  \w     71.00  97.00   0.50    0.05    --   74.09  15.00 150.00   52
 29  \w     74.00 113.00   0.50    0.05    --   74.09  15.00 120.00   78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1231696000
_diffrn_orient_matrix_UB_12      -0.0474673000
_diffrn_orient_matrix_UB_13      0.0422835000
_diffrn_orient_matrix_UB_21      -0.1387965000
_diffrn_orient_matrix_UB_22      -0.0555175000
_diffrn_orient_matrix_UB_23      -0.0296587000
_diffrn_orient_matrix_UB_31      0.2105328000
_diffrn_orient_matrix_UB_32      -0.0088195000
_diffrn_orient_matrix_UB_33      -0.0407192000
_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  0.0316
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            22600
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.859
_diffrn_reflns_theta_min         3.775
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.078
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52550
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.466
_exptl_crystal_description       block
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.219
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     396
_refine_ls_number_reflns         5116
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.362
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0490
_refine_ls_shift/su_max          0.089
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0737P)^2^+1.5896P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1381
_refine_ls_wR_factor_ref         0.1421
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4525
_reflns_number_total             5116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc05046d2.cif
_cod_data_source_block           l114
_cod_depositor_comments
'Adding full bibliography for 7251254--7251256.cif.'
_cod_database_code               7251256
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N F S Cl'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O3-H3
 0.86 with sigma of 0.01
 O5-C13 = O5-H5A
 1.38 with sigma of 0.01
3. Others
 Sof(H13A)=Sof(O5)=Sof(H5A)=1-FVAR(1)
 Sof(O2)=Sof(H2)=Sof(H13)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C13(H13), C13(H13A), C16(H16)
4.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C14(H14A,H14B), C17(H17A,H17B), C18(H18A,H18B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C4(H4), C5(H5), C7(H7), C10(H10), C21(H21), C23(H23), C25(H25),
 C27(H27), C28(H28)
4.d Tetrahedral OH refined with riding coordinates:
 O5(H5A)
4.e Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C30(H30A,H30B,H30C)
4.f Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              19666
_shelx_hkl_checksum              22593
_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 1.784
_oxdiff_exptl_absorpt_empirical_full_min 0.505