BF3·OEt2-Mediated Nucleophilic Fluorocyclization of Sulfonyl 3-Methylene-oxabenzocyclooctan-6-ones. Diastereocontrolled Synthesis of Benzofused Fluorooxabicyclo[4.2.1]nonanes
Hsueh, Nai-Chen; Chang, Meng-Yang; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01459A

data_7158869
_publ_section_title
;
 BF3&#x00B7;OEt2-Mediated Nucleophilic Fluorocyclization of Sulfonyl
 3-Methylene-oxabenzocyclooctan-6-ones. Diastereocontrolled Synthesis of
 Benzofused Fluorooxabicyclo[4.2.1]nonanes
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01459A
_journal_year                    2022
_chemical_formula_moiety         'C22 H25 F O3 S'
_chemical_formula_sum            'C22 H25 F O3 S'
_chemical_formula_weight         388.48
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-01-01
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2020-05-11 deposited with the CCDC.	2022-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                114.737(2)
_cell_angle_beta                 100.424(2)
_cell_angle_gamma                104.503(2)
_cell_formula_units_Z            4
_cell_length_a                   10.5216(3)
_cell_length_b                   14.9812(4)
_cell_length_c                   15.0603(3)
_cell_measurement_reflns_used    16189
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.8360
_cell_measurement_theta_min      2.1060
_cell_volume                     1974.08(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.36a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.36a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.36a (Rigaku OD, 2019)'
_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_temperature      113(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.943
_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    -70.00 -43.00   0.50   21.57    --   10.60 -36.00  37.00   54
  2  \w     12.00  37.00   0.50   21.57    --   10.60  36.00-166.00   50
  3  \w    -98.00 -71.00   0.50   21.57    --  -10.90 -36.00  37.00   54
  4  \w    -47.00 -12.00   0.50   21.57    --  -10.90 -36.00  37.00   70
  5  \w    -78.00  41.00   0.50   21.57    --   10.60 -57.00 -30.00  238
  6  \w    -16.00  13.00   0.50   21.57    --   10.60  82.00  60.00   58
  7  \w     -2.00  25.00   0.50   21.57    --   10.60  82.00 -90.00   54
  8  \w     42.00  99.00   0.50   21.57    --   10.60  82.00-120.00  114
  9  \w     48.00  75.00   0.50   21.57    --   10.60  82.00  60.00   54
 10  \w    -11.00  98.00   0.50   21.57    --   10.60  82.00 150.00  218
 11  \w    -12.00  17.00   0.50   21.57    --   10.60  82.00-120.00   58
 12  \w     -4.00  30.00   0.50   21.57    --   10.60  82.00  90.00   68
 13  \w    -19.00  36.00   0.50   21.57    --   10.60  57.00 150.00  110
 14  \w     52.00  77.00   0.50   21.57    --   10.60  57.00 150.00   50
 15  \w    -10.00  74.00   0.50   21.57    --   10.60  82.00 -60.00  168
 16  \w    -26.00  77.00   0.50   21.57    --  -10.90  82.00-180.00  206
 17  \w    -33.00  -6.00   0.50   21.57    --  -10.90 -77.00   0.00   54
 18  \w    -42.00 -17.00   0.50   21.57    --  -10.90 -77.00 -60.00   50
 19  \w    -44.00 -16.00   0.50   21.57    --  -10.90 -77.00 -30.00   56
 20  \w    -68.00  17.00   0.50   21.57    --  -10.90 -82.00-120.00  170
 21  \w    -92.00 -61.00   0.50   21.57    --  -10.90 -77.00 -60.00   62
 22  \w    -10.00  15.00   0.50   21.57    --  -10.90  36.00-166.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0200704000
_diffrn_orient_matrix_UB_12      -0.0369738000
_diffrn_orient_matrix_UB_13      0.0111404000
_diffrn_orient_matrix_UB_21      0.0528405000
_diffrn_orient_matrix_UB_22      0.0052792000
_diffrn_orient_matrix_UB_23      -0.0228045000
_diffrn_orient_matrix_UB_31      0.0471829000
_diffrn_orient_matrix_UB_32      0.0417200000
_diffrn_orient_matrix_UB_33      0.0486036000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0422
_diffrn_reflns_av_unetI/netI     0.0492
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            33783
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.076
_diffrn_reflns_theta_min         2.114
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.192
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57917
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.36a (Rigaku Oxford Diffraction, 2019)
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    1.307
_exptl_crystal_description       block
_exptl_crystal_F_000             824
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     493
_refine_ls_number_reflns         8215
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0613P)^2^+0.1245P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1083
_refine_ls_wR_factor_ref         0.1150
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6292
_reflns_number_total             8215
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01459a2.cif
_cod_data_source_block           exp_256
_cod_depositor_comments
;

2025-03-06
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_weight         194.24
_cod_original_formula_moiety         '0.5(C22 H25 F O3 S)'
_cod_original_formula_units_Z            8
_cod_original_cell_volume        1974.08(9)
_cod_original_formula_sum        'C11 H12.50 F0.50 O1.50 S0.50'
_cod_database_code               7158869
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_frames
;
011cfcb5ccf321f6041f735e120babbcce00025f46d
;
_diffrn_oxdiff_digest_hkl
;
0113b03b133e910161275d71d0324faedf3f93
;
_reflns_odcompleteness_completeness 99.22
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
2.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8), C29(H29), C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9B,H9A), C11(H11B,H11A), C12(H12B,H12A), C31(H31B,H31A), C33(H33B,H33A),
 C34(H34A,H34B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C17(H17), C18(H18),
 C24(H24), C25(H25), C26(H26), C27(H27), C36(H36), C37(H37), C39(H39), C40(H40)
2.d Idealised Me refined as rotating group:
 C20(H20C,H20B,H20A), C21(H21B,H21A,H21C), C22(H22A,H22C,H22B), C42(H42A,H42C,
 H42B), C43(H43B,H43A,H43C), C44(H44B,H44A,H44C)
;
_shelx_res_checksum              96802
_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 1.278
_oxdiff_exptl_absorpt_empirical_full_min 0.645