Access to Electron-Deficient 2,2-Disubstituted Chromanes: A Highly Regioselective One-Pot Synthesis via an Inverse-Electron-Demand [4 + 2] Cycloaddition of <i>ortho</i>-Quinone Methides.
Tanaka, Kenta; Kishimoto, Mami; Asada, Yosuke; Tanaka, Yuta; Hoshino, Yujiro; Honda, Kiyoshi; The Journal of organic chemistry 84 (2019) 13858–13870; doi:10.1021/acs.joc.9b02036

data_4033615
_publ_section_title
;
 Access to Electron-Deficient 2,2-Disubstituted Chromanes: A Highly
 Regioselective One-Pot Synthesis via an Inverse-Electron-Demand [4 + 2]
 Cycloaddition of <i>ortho</i>-Quinone Methides.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13858
_journal_page_last               13870
_journal_paper_doi               10.1021/acs.joc.9b02036
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C17 H16 N2 O7'
_chemical_formula_sum            'C17 H16 N2 O7'
_chemical_formula_weight         360.32
_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_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                86.965(4)
_cell_angle_beta                 79.616(3)
_cell_angle_gamma                78.971(3)
_cell_formula_units_Z            2
_cell_length_a                   7.6119(2)
_cell_length_b                   8.7039(4)
_cell_length_c                   13.0410(6)
_cell_measurement_reflns_used    3894
_cell_measurement_temperature    223
_cell_measurement_theta_max      70.4930
_cell_measurement_theta_min      3.4330
_cell_volume                     834.01(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (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_temperature      223
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.963
_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     78.00 104.00   0.50    0.50    --   24.00  38.00-120.00   52
  2  \w    -24.00  69.00   0.50    0.50    --   24.00 -82.00-150.00  186
  3  \w    -13.00  87.00   0.50    0.50    --   24.00 -38.00 -90.00  200
  4  \w    -14.00  48.00   0.50    0.50    --   24.00  82.00  90.00  124
  5  \w     30.00  57.00   0.50    0.50    --   24.00  38.00-120.00   54
  6  \w     65.00 107.00   0.50    0.50    --   24.00  77.00-120.00   84
  7  \w    -16.00  40.00   0.50    0.50    --   24.00  77.00-120.00  112
  8  \w    -24.00  22.00   0.50    0.50    --   24.00 -57.00  60.00   92
  9  \w    -40.00  19.00   0.50    0.50    --   24.00  38.00-120.00  118
 10  \w     78.00 104.00   0.50    0.58    --  102.70 -82.00   0.00   52
 11  \w     90.00 116.00   0.50    0.58    --  102.70 -82.00 -30.00   52
 12  \w     66.00 189.00   0.50    0.58    --  102.70  38.00 -30.00  246
 13  \w     42.00  68.00   0.50    0.58    --  102.70 -82.00 -30.00   52
 14  \w     19.00 121.00   0.50    0.58    --  102.70 -82.00-150.00  204
 15  \w     26.00 144.00   0.50    0.58    --  102.70 -82.00 -90.00  236
 16  \w     93.00 129.00   0.50    0.58    --  102.70 -82.00  90.00   72
 17  \w    167.00 192.00   0.50    0.58    --  102.70  38.00-180.00   50
 18  \w     23.00  49.00   0.50    0.58    --  102.70 -82.00-180.00   52
 19  \w     70.00  95.00   0.50    0.58    --  102.70 -82.00-180.00   50
 20  \w     38.00 107.00   0.50    0.58    --  102.70 -82.00  30.00  138
 21  \w     13.00 147.00   0.50    0.58    --  102.70 -82.00 120.00  268
 22  \w     18.00  90.00   0.50    0.58    --  102.70 -82.00  90.00  144
 23  \w     17.00 190.00   0.50    0.58    --  102.70  25.00  60.00  346
 24  \w     70.00  95.00   0.50    0.58    --  102.70  38.00-180.00   50
 25  \w     26.00  60.00   0.50    0.58    --  102.70 -50.00  60.00   68
 26  \w     66.00 141.00   0.50    0.58    --  102.70 -82.00 -60.00  150
 27  \w    116.00 192.00   0.50    0.58    --  102.70  38.00 -60.00  152
 28  \w     42.00  74.00   0.50    0.58    --  102.70  38.00 -60.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa dual offset/far'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0261571000
_diffrn_orient_matrix_UB_12      -0.1612965000
_diffrn_orient_matrix_UB_13      -0.0312402000
_diffrn_orient_matrix_UB_21      0.0378452000
_diffrn_orient_matrix_UB_22      0.0491901000
_diffrn_orient_matrix_UB_23      -0.1159222000
_diffrn_orient_matrix_UB_31      0.2042572000
_diffrn_orient_matrix_UB_32      -0.0639795000
_diffrn_orient_matrix_UB_33      -0.0038923000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0514
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            6556
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.641
_diffrn_reflns_theta_min         3.446
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.962
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40390
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.435
_exptl_crystal_description       block
_exptl_crystal_F_000             376
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.264
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3088
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0599
_refine_ls_R_factor_gt           0.0550
_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^)+(0.1163P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1608
_refine_ls_wR_factor_ref         0.1698
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2669
_reflns_number_total             3088
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02036_si_002.cif
_cod_data_source_block           exp_279
_cod_depositor_comments
'Adding full bibliography for 4033613--4033615.cif.'
_cod_database_code               4033615
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.645
_diffrn_oxdiff_ac3_digest_frames
;
0144fdae7f6a9ced2aeb0d9523be6aeecd00033b1a2
;
_diffrn_oxdiff_ac3_digest_hkl
;
01cc83e9061aaf9cbada6f1131576874cfefa1
;
_reflns_odcompleteness_completeness 98.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H00B(0.041) H00E(0.04) H00A(0.04) H00C(0.04) H00H(0.046)
 H00I(0.045) H00J(0.047) H00M(0.048) H00N(0.056) H00O(0.061) H00D(0.083)
 H00F(0.083) H00G(0.083) H00K(0.086) H00L(0.086) H00P(0.086)
 Fixed X: H00B(0.13638) H00E(-0.014708) H00A(0.127051) H00C(0.319208)
 H00H(0.490781) H00I(0.597698) H00J(0.474769) H00M(0.752979) H00N(0.120189)
 H00O(0.2744) H00D(-0.132676) H00F(0.037454) H00G(-0.039394) H00K(0.119108)
 H00L(0.14506) H00P(-0.052988)
 Fixed Y: H00B(-0.013342) H00E(0.250031) H00A(0.298718) H00C(0.211808)
 H00H(0.360694) H00I(0.415286) H00J(0.163347) H00M(0.539047) H00N(0.633266)
 H00O(0.758439) H00D(0.102982) H00F(0.067271) H00G(-0.072445) H00K(0.633768)
 H00L(0.722055) H00P(0.718171)
 Fixed Z: H00B(0.561676) H00E(0.713318) H00A(0.848727) H00C(0.790983)
 H00H(0.439928) H00I(0.719745) H00J(0.330345) H00M(0.819103) H00N(0.879245)
 H00O(0.978396) H00D(0.845493) H00F(0.903062) H00G(0.864947) H00K(0.582653)
 H00L(0.680458) H00P(0.660092)
;
_shelx_res_checksum              11198
_shelx_hkl_checksum              34373
_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 2.703
_oxdiff_exptl_absorpt_empirical_full_min 0.510