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_7251254
_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         'C21 H17 F6 N O'
_chemical_formula_sum            'C21 H17 F6 N O'
_chemical_formula_weight         413.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-31
_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                 109.638(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1569(2)
_cell_length_b                   22.3534(4)
_cell_length_c                   9.6077(2)
_cell_measurement_reflns_used    4616
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      73.9750
_cell_measurement_theta_min      3.9120
_cell_volume                     1852.19(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      169.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.968
_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     13.00  86.00   1.00    1.00    --   40.73  57.00  90.00   73
  2  \w     79.00 161.00   1.00    1.00    --  108.20  61.00   0.00   82
  3  \w    108.00 135.00   1.00    1.00    --  108.20 -30.00   0.00   27
  4  \w    113.00 141.00   1.00    1.00    --  108.20 -77.00-150.00   28
  5  \w     37.00 101.00   1.00    1.00    --  108.20 -94.00-150.00   64
  6  \w     25.00  96.00   1.00    1.00    --   40.73-125.00-150.00   71
  7  \w     32.00  71.00   1.00    1.00    --  108.20 -30.00   0.00   39
  8  \w     48.00 120.00   1.00    1.00    --  108.20-125.00 120.00   72
  9  \w    -61.00  34.00   1.00    1.00    --  -40.73  38.00-120.00   95
 10  \w     97.00 148.00   1.00    1.00    --  108.20 125.00   0.00   51
 11  \w     96.00 148.00   1.00    1.00    --  108.20 125.00 -60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0452963000
_diffrn_orient_matrix_UB_12      0.0610051000
_diffrn_orient_matrix_UB_13      0.0482221000
_diffrn_orient_matrix_UB_21      -0.1326142000
_diffrn_orient_matrix_UB_22      -0.0301427000
_diffrn_orient_matrix_UB_23      0.0389473000
_diffrn_orient_matrix_UB_31      0.1107106000
_diffrn_orient_matrix_UB_32      -0.0110395000
_diffrn_orient_matrix_UB_33      0.1585230000
_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  0.0258
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            6944
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.224
_diffrn_reflns_theta_min         3.955
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.158
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.23124
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.482
_exptl_crystal_description       block
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.278
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.054
_refine_ls_extinction_coef       0.0086(7)
_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   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         3645
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0472
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0847P)^2^+0.3240P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1317
_refine_ls_wR_factor_ref         0.1366
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3254
_reflns_number_total             3645
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5gc05046d2.cif
_cod_data_source_block           w12
_cod_depositor_comments
'Adding full bibliography for 7251254--7251256.cif.'
_cod_database_code               7251254
_shelx_shelxl_version_number     2018/3
_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.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C14(H14A,H14B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C16(H16), C17(H17), C19(H19), C20(H20)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              58431
_shelx_hkl_checksum              88481
_olex2_date_sample_data_collection 2024-10-30
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.166
_oxdiff_exptl_absorpt_empirical_full_min 0.490