Asymmetric synthesis of spiro-structural 2,3-dihydrobenzofurans via the bifunctional phosphonium salt-promoted [4 + 1] cyclization of ortho-quinone methides with α-bromoketones
Zhang, Song; Yu, Xiaojun; Pan, Jianke; Jiang, Chunhui; Zhang, Hongsu; Wang, Tianli; Organic Chemistry Frontiers 6 (2019) 3799–; doi:10.1039/C9QO01096C

data_1555182
_publ_section_title
;
 Asymmetric synthesis of spiro-structural 2,3-dihydrobenzofurans via the
 bifunctional phosphonium salt-promoted [4 + 1] cyclization of
 ortho-quinone methides with \a-bromoketones
;
_journal_issue                   22
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              3799
_journal_paper_doi               10.1039/C9QO01096C
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H18 O5'
_chemical_formula_sum            'C25 H18 O5'
_chemical_formula_weight         398.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-10-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2018-10-29 deposited with the CCDC.	2019-10-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.620(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.6007(8)
_cell_length_b                   5.7368(5)
_cell_length_c                   15.0074(10)
_cell_measurement_reflns_used    2809
_cell_measurement_temperature    293.8(4)
_cell_measurement_theta_max      71.7190
_cell_measurement_theta_min      3.8570
_cell_volume                     978.29(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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_environment      air
_diffrn_ambient_temperature      293.8(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_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   -107.00  -4.00   1.00    1.00    --  -36.04 -18.00-133.00  103
  2  \w   -105.00 -17.00   1.00    1.00    --  -36.04 -38.00 150.00   88
  3  \w     19.00 103.00   1.00    1.00    --   36.04  57.00-150.00   84
  4  \w     17.00 105.00   1.00    1.00    --   36.04  38.00-150.00   88
  5  \w     17.00 105.00   1.00    1.00    --   36.04  38.00  60.00   88
  6  \w    -32.00  63.00   1.00    1.00    --   36.04 -77.00 120.00   95
  7  \w      9.00 104.00   1.00    1.00    --   36.04  77.00 150.00   95
  8  \w    -33.00  55.00   1.00    1.00    --   36.04 -38.00 -30.00   88
  9  \w     19.00 103.00   1.00    1.00    --   36.04  57.00 120.00   84
 10  \w     23.00  89.00   1.00    1.00    --   36.04-125.00 -60.00   66
 11  \w     41.00 135.00   1.00    2.60    --  108.71 -77.00 -60.00   94
 12  \w     87.00 178.00   1.00    2.60    --  108.71  30.00-150.00   91
 13  \w     82.00 176.00   1.00    2.60    --  108.71  77.00 150.00   94
 14  \w     91.00 176.00   1.00    2.60    --  108.71  61.00  90.00   85
 15  \w     87.00 178.00   1.00    2.60    --  108.71  30.00-180.00   91
 16  \w     87.00 160.00   1.00    2.60    --  108.71  30.00 120.00   73
 17  \w    136.00 163.00   1.00    2.60    --  108.71  77.00-180.00   27
 18  \w    136.00 176.00   1.00    2.60    --  108.71  61.00  60.00   40
 19  \w     82.00 109.00   1.00    2.60    --  108.71  77.00-180.00   27
 20  \w     93.00 118.00   1.00    2.60    --  108.71  61.00 120.00   25
 21  \w     92.00 121.00   1.00    2.60    --  108.71  61.00 150.00   29
 22  \w     95.00 122.00   1.00    2.60    --  108.71  30.00  90.00   27
 23  \w     71.00 100.00   1.00    2.60    --  108.71  15.00 120.00   29
 24  \w     92.00 119.00   1.00    2.60    --  108.71  61.00  60.00   27
 25  \w     65.00  92.00   1.00    2.60    --  108.71 -94.00 120.00   27
 26  \w     88.00 117.00   1.00    2.60    --  108.71  30.00 150.00   29
 27  \w     82.00 108.00   1.00    2.60    --  108.71  77.00 120.00   26
 28  \w    124.00 175.00   1.00    2.60    --  108.71  77.00 120.00   51
 29  \w     83.00 115.00   1.00    2.60    --  108.71  77.00  60.00   32
 30  \w     91.00 150.00   1.00    2.60    --  108.71  61.00  30.00   59
 31  \w     96.00 123.00   1.00    2.60    --  108.71  45.00 150.00   27
 32  \w     93.00 122.00   1.00    2.60    --  108.71  61.00-180.00   29
 33  \w     83.00 175.00   1.00    2.60    --  108.71  77.00  30.00   92
 34  \w     83.00 108.00   1.00    2.60    --  108.71  77.00  90.00   25
 35  \w    125.00 173.00   1.00    2.60    --  108.71  77.00  90.00   48
 36  \w     71.00  96.00   1.00    2.60    --  108.71  15.00-120.00   25
 37  \w     39.00 111.00   1.00    2.60    --  108.71-111.00 -90.00   72
 38  \w     61.00  88.00   1.00    2.60    --  108.71 -94.00-180.00   27
 39  \w    142.00 169.00   1.00    2.60    --  108.71 111.00  60.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1219648000
_diffrn_orient_matrix_UB_12      -0.0425156000
_diffrn_orient_matrix_UB_13      0.0229010000
_diffrn_orient_matrix_UB_21      0.0514955000
_diffrn_orient_matrix_UB_22      0.0491958000
_diffrn_orient_matrix_UB_23      0.1010812000
_diffrn_orient_matrix_UB_31      -0.0295141000
_diffrn_orient_matrix_UB_32      0.2605466000
_diffrn_orient_matrix_UB_33      -0.0152004000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            10155
_diffrn_reflns_point_group_measured_fraction_full 0.907
_diffrn_reflns_point_group_measured_fraction_max 0.882
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.180
_diffrn_reflns_theta_min         3.890
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.773
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53136
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.352
_exptl_crystal_description       needle
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 1053 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3452
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0579
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1151P)^2^+0.0915P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1605
_refine_ls_wR_factor_ref         0.1702
_reflns_Friedel_coverage         0.627
_reflns_Friedel_fraction_full    0.792
_reflns_Friedel_fraction_max     0.760
_reflns_number_gt                3068
_reflns_number_total             3452
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo01096c2.cif
_cod_data_source_block           wtl-zsrsp2
_cod_database_code               1555182
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00I(H00I)
2.b Aromatic/amide H refined with riding coordinates:
 C006(H006), C00A(H00A), C00D(H00D), C00J(H00J), C00K(H00K), C00L(H00L),
 C00M(H00M), C00N(H00N), C00P(H00P), C00Q(H00Q), C00T(H00T)
2.c Idealised Me refined as rotating group:
 C00S(H00B,H00C,H00E), C00U(H00F,H00G,H00H)
;
_shelx_res_checksum              22855
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2018-10-29
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.619
_oxdiff_exptl_absorpt_empirical_full_min 0.612