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_7158874
_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_absolute_configuration ad
_chemical_formula_moiety         'C19 H18 F2 O3 S'
_chemical_formula_sum            'C19 H18 F2 O3 S'
_chemical_formula_weight         364.39
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-27
_audit_creation_method
; 
Olex2 1.2 
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506) 
;
_audit_update_record
;
2020-05-11 deposited with the CCDC.	2022-09-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.88630(10)
_cell_length_b                   9.4890(2)
_cell_length_c                   29.6414(7)
_cell_measurement_reflns_used    19556
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      26.9770
_cell_measurement_theta_min      2.2460
_cell_volume                     1655.62(6)
_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  'XL (Sheldrick, 2008)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.975
_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    -16.00  23.00   0.50    3.05    --   10.60  -8.00 145.00   78 
  2  \w     26.00  53.00   0.50    3.05    --  -10.90  -8.00 145.00   54 
  3  \w    -21.00   5.00   0.50    3.05    --  -10.90   8.00 -40.00   52 
  4  \w    -86.00 -60.00   0.50    3.05    --  -10.90  -8.00 145.00   52 
  5  \w     -1.00  98.00   0.50    3.05    --   10.60  82.00  30.00  198 
  6  \w     49.00  75.00   0.50    3.05    --   10.60  77.00-120.00   52 
  7  \w     26.00  51.00   0.50    3.05    --   10.60  77.00  60.00   50 
  8  \w    -14.00  11.00   0.50    3.05    --   10.60   8.00 -40.00   50 
  9  \w    -10.00  52.00   0.50    3.05    --   10.60  82.00-180.00  124 
 10  \w     28.00  67.00   0.50    3.05    --   10.60  82.00 150.00   78 
 11  \w     -5.00  39.00   0.50    3.05    --   10.60  82.00   0.00   88 
 12  \w     -5.00 100.00   0.50    3.05    --   10.60  82.00 -60.00  210 
 13  \w    -17.00  40.00   0.50    3.05    --   10.60  82.00-120.00  114 
 14  \w    -17.00  38.00   0.50    3.05    --   10.60  82.00  90.00  110 
 15  \w    -74.00 -48.00   0.50    3.05    --   10.60 -77.00-150.00   52 
 16  \w    -30.00  -5.00   0.50    3.05    --   10.60 -77.00-150.00   50 
 17  \w     21.00  46.00   0.50    3.05    --   10.60  77.00   0.00   50 
 18  \w    -36.00  79.00   0.50    3.05    --  -10.90  82.00 -30.00  230 
 19  \w   -100.00 -44.00   0.50    3.05    --  -10.90 -82.00 150.00  112 
 20  \w    -29.00  79.00   0.50    3.05    --  -10.90  77.00-120.00  216 
 21  \w    -86.00  -9.00   0.50    3.05    --  -10.90 -77.00  90.00  154 
;
_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      0.0575240000
_diffrn_orient_matrix_UB_12      -0.0654078000
_diffrn_orient_matrix_UB_13      -0.0017093000
_diffrn_orient_matrix_UB_21      -0.1057599000
_diffrn_orient_matrix_UB_22      -0.0352673000
_diffrn_orient_matrix_UB_23      -0.0020853000
_diffrn_orient_matrix_UB_31      0.0050766000
_diffrn_orient_matrix_UB_32      0.0077708000
_diffrn_orient_matrix_UB_33      -0.0237887000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            31130
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.000
_diffrn_reflns_theta_min         2.254
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.232
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42029
_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    1.462
_exptl_crystal_description       block
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.324
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
; 
 Flack x determined using 1313 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         3504
_refine_ls_number_restraints     115
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0314
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0377P)^2^+0.8298P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0767
_refine_ls_wR_factor_ref         0.0780
_reflns_Friedel_coverage         0.686
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.949
_reflns_number_gt                3349
_reflns_number_total             3504
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01459a2.cif
_cod_data_source_block           nc1204nb
_cod_database_code               7158874
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C19 H18 F2 O3 S1'
_diffrn_oxdiff_digest_frames
; 
015b094a7991dd23a321443653c4a036bc00025941b 
;
_diffrn_oxdiff_digest_hkl
; 
0156f760f6395405aee6967eebea7ff7d1ed06 
;
_reflns_odcompleteness_completeness 99.75
_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. Rigid bond restraints 
 F1, C2 
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 8 
3. Uiso/Uaniso restraints and constraints 
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim 
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) 
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, 
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) 
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, 
Uanis(C19) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001 
4.a Ternary CH refined with riding coordinates: 
 C4(H4), C5(H5) 
4.b Secondary CH2 refined with riding coordinates: 
 C1(H1A,H1B), C3(H3A,H3B), C12(H12A,H12B) 
4.c Aromatic/amide H refined with riding coordinates: 
 C7(H7), C9(H9), C10(H10), C14(H14), C15(H15), C17(H17), C18(H18) 
4.d Idealised Me refined as rotating group: 
 C19(H19A,H19B,H19C) 
;
_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 1.897
_oxdiff_exptl_absorpt_empirical_full_min 0.701