Base-promoted cyclization of <i>ortho</i>-hydroxyacetophenones with <i>in situ</i> generated cyclopropenes: diastereoselective access to spirobenzo[<i>b</i>]oxepines and related precursors.
Prakash, Meher; Samanta, Sampak; Organic & biomolecular chemistry 21 (2023) 2001–2014; doi:10.1039/d3ob00077j

data_7159154
_publ_section_title
;
 Base-promoted cyclization of <i>ortho</i>-hydroxyacetophenones with <i>in
 situ</i> generated cyclopropenes: diastereoselective access to
 spirobenzo[<i>b</i>]oxepines and related precursors.
;
_journal_issue                   9
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2001
_journal_page_last               2014
_journal_paper_doi               10.1039/d3ob00077j
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C19 H14 O4'
_chemical_formula_sum            'C19 H14 O4'
_chemical_formula_weight         306.320
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2022-12-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-30 deposited with the CCDC.	2023-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                85.100(6)
_cell_angle_beta                 81.305(6)
_cell_angle_gamma                68.735(7)
_cell_formula_units_Z            2
_cell_length_a                   8.5674(6)
_cell_length_b                   9.4995(7)
_cell_length_c                   9.9500(7)
_cell_measurement_reflns_used    3092
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.8090
_cell_measurement_theta_min      3.7130
_cell_volume                     745.57(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0309
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9978
_diffrn_measured_fraction_theta_max 0.8840
_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    -44.00  50.00   1.00   50.00    --   18.09 -81.00-110.00   94
  2  \w    -15.00  10.00   1.00   50.00    --  -19.42 -81.00-110.00   25
  3  \w    -51.00 -19.00   1.00   50.00    --  -19.42  81.00  12.00   32
  4  \w    -50.00  37.00   1.00   50.00    --   18.09 -57.00   0.00   87
  5  \w    -52.00  46.00   1.00   50.00    --   18.09 -77.00 150.00   98
  6  \w    -11.00  18.00   1.00   50.00    --   18.09  77.00 150.00   29
  7  \w    -41.00  48.00   1.00   50.00    --  -19.42  57.00 120.00   89
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0663301000
_diffrn_orient_matrix_UB_12      0.0178886000
_diffrn_orient_matrix_UB_13      -0.0406487000
_diffrn_orient_matrix_UB_21      -0.0400347000
_diffrn_orient_matrix_UB_22      -0.0408175000
_diffrn_orient_matrix_UB_23      0.0469237000
_diffrn_orient_matrix_UB_31      -0.0449938000
_diffrn_orient_matrix_UB_32      0.0666384000
_diffrn_orient_matrix_UB_33      0.0367718000
_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  0.0307
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.9978
_diffrn_reflns_Laue_measured_fraction_max 0.8840
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            6876
_diffrn_reflns_point_group_measured_fraction_full 0.9978
_diffrn_reflns_point_group_measured_fraction_max 0.8840
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.94
_diffrn_reflns_theta_min         3.05
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40828
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.364
_exptl_crystal_description       block
_exptl_crystal_F_000             320.224
_refine_diff_density_max         0.2762
_refine_diff_density_min         -0.2872
_refine_diff_density_rms         0.0618
_refine_ls_d_res_high            0.7344
_refine_ls_d_res_low             6.6877
_refine_ls_extinction_coef       0.033(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0415
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    26
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3484
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0415
_refine_ls_R_factor_all          0.0719
_refine_ls_R_factor_gt           0.0575
_refine_ls_shift/su_max          -0.0003
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0409P)^2^+0.4378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1447
_refine_ls_wR_factor_ref         0.1533
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -11
_reflns_limit_k_max              12
_reflns_limit_k_min              -11
_reflns_limit_l_max              13
_reflns_limit_l_min              0
_reflns_number_gt                2696
_reflns_number_total             3484
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3ob00077j2.cif
_cod_data_source_block           SS45
_cod_depositor_comments
'Adding full bibliography for 7159154--7159155.cif.'
_cod_database_code               7159154
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C009(H009)
2.b Secondary CH2 refined with riding coordinates:
 C00G(H00a,H00e), C00I(H00g,H00i)
2.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00H(H00H), C00J(H00J), C00C(H00C), C00F(H00F), C00M(H00M),
 C00N(H00N), C00L(H00L), C00D(H00D)
;
_olex2_date_sample_data_collection 2022-12-29
_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 3.874
_oxdiff_exptl_absorpt_empirical_full_min 0.488