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_4033614
_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                112.025(2)
_cell_angle_beta                 102.5850(10)
_cell_angle_gamma                98.478(2)
_cell_formula_units_Z            2
_cell_length_a                   9.1504(2)
_cell_length_b                   9.1640(2)
_cell_length_c                   11.3246(2)
_cell_measurement_reflns_used    5316
_cell_measurement_temperature    223
_cell_measurement_theta_max      70.5320
_cell_measurement_theta_min      4.4010
_cell_volume                     831.15(3)
_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 0.987
_diffrn_measured_fraction_theta_max 0.968
_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      0.00  44.00   0.50    0.50    --   24.00 -57.00  60.00   88
  2  \w     11.00  59.00   0.50    0.50    --   24.00 -77.00 150.00   96
  3  \w     -4.00  69.00   0.50    0.50    --   24.00 -82.00-120.00  146
  4  \w     28.00  65.00   0.50    0.50    --   24.00 -77.00 -90.00   74
  5  \w    -39.00   8.00   0.50    0.50    --   24.00 -77.00 150.00   94
  6  \w     12.00  38.00   0.50    0.50    --   24.00  57.00-180.00   52
  7  \w    -64.00  33.00   0.50    0.50    --   24.00 -77.00-180.00  194
  8  \w     -1.00  66.00   0.50    0.50    --   24.00 -82.00   0.00  134
  9  \w    -47.00 -17.00   0.50    0.50    --   24.00 -82.00-120.00   60
 10  \w    -56.00  18.00   0.50    0.50    --   24.00 -77.00 -90.00  148
 11  \w     80.00 145.00   0.50    0.50    --  102.70 -82.00-150.00  130
 12  \w     74.00 100.00   0.50    0.50    --  102.70 -82.00  90.00   52
 13  \w     13.00  92.00   0.50    0.50    --  102.70 -12.00 -30.00  158
 14  \w     98.00 190.00   0.50    0.50    --  102.70 -12.00 -30.00  184
 15  \w     26.00  65.00   0.50    0.50    --  102.70 -82.00  90.00   78
 16  \w    111.00 192.00   0.50    0.50    --  102.70 -12.00-120.00  162
 17  \w     40.00  66.00   0.50    0.50    --  102.70 -63.00   0.00   52
 18  \w    100.00 167.00   0.50    0.50    --  102.70 -38.00  30.00  134
 19  \w     23.00  84.00   0.50    0.50    --  102.70 -38.00  30.00  122
 20  \w     58.00 120.00   0.50    0.50    --  102.70 -82.00 -30.00  124
 21  \w     22.00 107.00   0.50    0.50    --  102.70 -82.00  30.00  170
 22  \w     13.00  99.00   0.50    0.50    --  102.70 -12.00-120.00  172
 23  \w     16.00  91.00   0.50    0.50    --  102.70 -82.00 150.00  150
 24  \w     90.00 148.00   0.50    0.50    --  102.70 -82.00-120.00  116
 25  \w     13.00  69.00   0.50    0.50    --  102.70 -82.00-120.00  112
 26  \w     94.00 134.00   0.50    0.50    --  102.70 -63.00   0.00   80
 27  \w     28.00 143.00   0.50    0.50    --  102.70 -82.00-180.00  230
 28  \w     19.00  98.00   0.50    0.50    --  102.70 -50.00-180.00  158
 29  \w    111.00 137.00   0.50    0.50    --  102.70 -50.00-180.00   52
 30  \w    107.00 132.00   0.50    0.50    --  102.70 -50.00 150.00   50
 31  \w     32.00  57.00   0.50    0.50    --  102.70 -50.00 150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1209790000
_diffrn_orient_matrix_UB_12      -0.0904226000
_diffrn_orient_matrix_UB_13      -0.0451923000
_diffrn_orient_matrix_UB_21      -0.1113463000
_diffrn_orient_matrix_UB_22      -0.0885705000
_diffrn_orient_matrix_UB_23      -0.1431065000
_diffrn_orient_matrix_UB_31      0.0690163000
_diffrn_orient_matrix_UB_32      0.1382693000
_diffrn_orient_matrix_UB_33      -0.0333226000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0210
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            6826
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.614
_diffrn_reflns_theta_min         4.412
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.966
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76571
_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    1.440
_exptl_crystal_description       plate
_exptl_crystal_F_000             376
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         3086
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.0493
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0713P)^2^+0.1879P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1238
_refine_ls_wR_factor_ref         0.1259
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2865
_reflns_number_total             3086
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02036_si_001.cif
_cod_data_source_block           exp_288
_cod_depositor_comments
'Adding full bibliography for 4033613--4033615.cif.'
_cod_database_code               4033614
_shelx_shelxl_version_number     2017/1
_diffrn_oxdiff_ac3_digest_frames
;
0192fc3ad9ca366e933e3bc088d8c0d0a0000394ff3
;
_diffrn_oxdiff_ac3_digest_hkl
;
0148a83521e16f8068445dcff98f98dd1a9739
;
_reflns_odcompleteness_completeness 98.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H00F(0.043) H00G(0.046) H00H(0.049) H00I(0.044) H00J(0.046)
 H00A(0.046) H00B(0.046) H00L(0.052) H00N(0.046) H00O(0.053) H00C(0.076)
 H00D(0.076) H00E(0.076) H00K(0.09) H00M(0.09) H00P(0.09)
 Fixed X: H00F(0.717668) H00G(0.343189) H00H(0.624051) H00I(0.880098)
 H00J(0.583981) H00A(0.862212) H00B(0.978423) H00L(0.978589) H00N(0.274272)
 H00O(1.016242) H00C(0.579695) H00D(0.712271) H00E(0.682821) H00K(1.094989)
 H00M(1.144982) H00P(1.158237)
 Fixed Y: H00F(0.814989) H00G(0.681093) H00H(0.402612) H00I(0.673194)
 H00J(0.503201) H00A(0.591937) H00B(0.761884) H00L(0.85407) H00N(0.741976)
 H00O(0.757858) H00C(0.949245) H00D(1.1041) H00E(0.951063) H00K(0.840475)
 H00M(0.862136) H00P(1.015398)
 Fixed Z: H00F(-0.073178) H00G(0.112629) H00H(0.505073) H00I(0.058701)
 H00J(0.343842) H00A(0.214848) H00B(0.306874) H00L(0.553439) H00N(-0.069737)
 H00O(0.717233) H00C(0.389359) H00D(0.489527) H00E(0.520333) H00K(0.065817)
 H00M(0.214118) H00P(0.182684)
;
_shelx_res_checksum              85317
_shelx_hkl_checksum              33466
_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 1.259
_oxdiff_exptl_absorpt_empirical_full_min 0.709