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_7159155
_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         'C22 H18 O3'
_chemical_formula_sum            'C22 H18 O3'
_chemical_formula_weight         330.386
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_Int_Tables_number      15
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-01-31 deposited with the CCDC.	2023-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.814(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.8421(3)
_cell_length_b                   14.4124(5)
_cell_length_c                   20.4372(7)
_cell_measurement_reflns_used    4145
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.4480
_cell_measurement_theta_min      4.4170
_cell_volume                     3414.19(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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 1.0000
_diffrn_measured_fraction_theta_max 0.9794
_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    -35.00  14.00   1.00   11.00    --    0.00  91.00 178.00   49
  2  \w     -5.00  21.00   1.00   11.00    --    0.00 -91.00  64.00   26
  3  \w     16.00  91.00   1.00   11.00    --   54.00 -91.00  64.00   75
  4  \w    115.00 141.00   1.00   11.00    --  108.00  91.00 178.00   26
  5  \w     39.00 146.00   1.00   11.00    --  108.00 -91.00  64.00  107
  6  \w    -62.00 -32.00   1.00   11.00    --    0.00 -77.00   0.00   30
  7  \w    -25.00  26.00   1.00   11.00    --    0.00 -77.00   0.00   51
  8  \w     23.00  63.00   1.00   11.00    --    0.00  57.00 -90.00   40
  9  \w     25.00 121.00   1.00   11.00    --   54.00  77.00 -30.00   96
 10  \w     38.00 103.00   1.00   11.00    --   54.00-125.00 -60.00   65
 11  \w     44.00 112.00   1.00   11.00    --   54.00  57.00 120.00   68
 12  \w     42.00 118.00   1.00   11.00    --   54.00  38.00 -90.00   76
 13  \w     39.00 110.00   1.00   11.00    --   54.00  57.00  30.00   71
 14  \w     34.00  60.00   1.00   11.00    --   54.00-125.00-180.00   26
 15  \w      4.00  47.00   1.00   11.00    --   54.00 -99.00-150.00   43
 16  \w     74.00 168.00   1.00   11.00    --  108.00  25.00-120.00   94
 17  \w    151.00 176.00   1.00   11.00    --  108.00  63.00   0.00   25
 18  \w    141.00 171.00   1.00   11.00    --  108.00 111.00  90.00   30
 19  \w     66.00 106.00   1.00   11.00    --  108.00-111.00 -60.00   40
 20  \w    110.00 136.00   1.00   11.00    --  108.00 -25.00  30.00   26
 21  \w     41.00 124.00   1.00   11.00    --  108.00 -50.00  30.00   83
 22  \w     74.00 176.00   1.00   11.00    --  108.00  25.00 -60.00  102
 23  \w    153.00 178.00   1.00   11.00    --  108.00 111.00  60.00   25
 24  \w     84.00 153.00   1.00   11.00    --  108.00  77.00 150.00   69
 25  \w     46.00 110.00   1.00   11.00    --  108.00-111.00-120.00   64
 26  \w     56.00 113.00   1.00   11.00    --  108.00-111.00  30.00   57
 27  \w     45.00 117.00   1.00   11.00    --  108.00 -38.00 -60.00   72
 28  \w     40.00  81.00   1.00   11.00    --  108.00-111.00 -90.00   41
 29  \w     45.00  83.00   1.00   11.00    --  108.00 -25.00  30.00   38
 30  \w     44.00 133.00   1.00   11.00    --  108.00 -38.00-150.00   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      0.1153684000
_diffrn_orient_matrix_UB_12      0.0427887000
_diffrn_orient_matrix_UB_13      0.0358780000
_diffrn_orient_matrix_UB_21      -0.0033853000
_diffrn_orient_matrix_UB_22      0.0669543000
_diffrn_orient_matrix_UB_23      -0.0590969000
_diffrn_orient_matrix_UB_31      -0.0659159000
_diffrn_orient_matrix_UB_32      0.0714469000
_diffrn_orient_matrix_UB_33      0.0339876000
_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  0.0996
_diffrn_reflns_av_unetI/netI     0.0638
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.9794
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            12340
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.9794
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         71.66
_diffrn_reflns_theta_min         4.42
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.680
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25768
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             1396.638
_refine_diff_density_max         0.3462
_refine_diff_density_min         -0.2904
_refine_diff_density_rms         0.0872
_refine_ls_d_res_high            0.8122
_refine_ls_d_res_low             10.0021
_refine_ls_extinction_coef       0.0024(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0358
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    31
_refine_ls_number_parameters     229
_refine_ls_number_reflns         3284
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0358
_refine_ls_R_factor_all          0.0876
_refine_ls_R_factor_gt           0.0690
_refine_ls_shift/su_max          -0.0005
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1255P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1824
_refine_ls_wR_factor_ref         0.2176
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -14
_reflns_limit_k_max              17
_reflns_limit_k_min              0
_reflns_limit_l_max              25
_reflns_limit_l_min              0
_reflns_number_gt                2308
_reflns_number_total             3284
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d3ob00077j2.cif
_cod_data_source_block           MP1
_cod_depositor_comments
'Adding full bibliography for 7159154--7159155.cif.'
_cod_database_code               7159155
_chemical_oxdiff_formula         'C22 H18 O3'
_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 Secondary CH2 refined with riding coordinates:
 C00N(H00b,H00c)
2.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00A(H00A), C00H(H00H), C00M(H00M), C00L(H00L), C00F(H00F),
 C00G(H00G), C00K(H00K), C00J(H00J), C00D(H00D)
2.c Idealised Me refined as rotating group:
 C00O(H00e,H00i,H00n), C00P(H00o,H00p,H00q)
;
_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 7.795
_oxdiff_exptl_absorpt_empirical_full_min 0.200