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_4033613
_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         'C16 H15 N O4'
_chemical_formula_sum            'C16 H15 N O4'
_chemical_formula_weight         285.29
_chemical_name_common            4-methoxy-6-nitro-2-phenylchromane
_chemical_name_systematic        4-methoxy-6-nitro-2-phenylchromane
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.58200(10)
_cell_length_b                   12.21250(10)
_cell_length_c                   29.8274(3)
_cell_measurement_reflns_used    6599
_cell_measurement_temperature    223
_cell_measurement_theta_max      70.2710
_cell_measurement_theta_min      3.1130
_cell_volume                     2761.87(5)
_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_pressure         101.3
_diffrn_ambient_temperature      223
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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    -67.00 -42.00   0.50    0.50    --  -20.00 -80.00 -98.00   50
  2  \w     21.00  46.00   0.50    0.50    --   24.00  41.00-138.00   50
  3  \w    -23.00   2.00   0.50    0.50    --   24.00 -80.00 -98.00   50
  4  \w      2.00  27.00   0.50    0.50    --   24.00 -41.00  68.00   50
  5  \w    124.00 149.00   0.50    0.58    --  102.70  41.00-138.00   50
  6  \w     69.00  99.00   0.50    0.58    --  102.70 -80.00 -98.00   60
  7  \w    107.00 132.00   0.50    0.58    --  102.70  80.00  25.00   50
  8  \w     57.00  82.00   0.50    0.58    --  102.70 -41.00  68.00   50
  9  \w    -10.00  90.00   0.50    0.50    --   24.00  57.00 -30.00  200
 10  \w     29.00  65.00   0.50    0.50    --   24.00  57.00 -90.00   72
 11  \w    -63.00  59.00   0.50    0.50    --   24.00 -77.00  90.00  244
 12  \w     86.00 111.00   0.50    0.58    --  102.70  50.00  90.00   50
 13  \w     18.00 115.00   0.50    0.58    --  102.70 -63.00 -90.00  194
 14  \w     39.00 188.00   0.50    0.58    --  102.70  38.00-180.00  298
 15  \w     14.00 146.00   0.50    0.58    --  102.70  25.00   0.00  264
 16  \w    119.00 154.00   0.50    0.58    --  102.70  50.00 120.00   70
 17  \w     79.00 105.00   0.50    0.58    --  102.70  50.00 120.00   52
;
_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      0.1195923000
_diffrn_orient_matrix_UB_12      -0.0532335000
_diffrn_orient_matrix_UB_13      -0.0355970000
_diffrn_orient_matrix_UB_21      0.1641895000
_diffrn_orient_matrix_UB_22      0.0372532000
_diffrn_orient_matrix_UB_23      0.0262779000
_diffrn_orient_matrix_UB_31      -0.0023269000
_diffrn_orient_matrix_UB_32      -0.1081433000
_diffrn_orient_matrix_UB_33      0.0266571000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0283
_diffrn_reflns_av_unetI/netI     0.0213
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            10022
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.760
_diffrn_reflns_theta_min         2.963
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.822
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65408
_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    1.372
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.6
_refine_diff_density_max         0.436
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.168
_refine_ls_extinction_coef       0.0084(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2630
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0768P)^2^+0.3044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1237
_refine_ls_wR_factor_ref         0.1265
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2398
_reflns_number_total             2630
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02036_si_003.cif
_cod_data_source_block           exp_332
_cod_depositor_comments
'Adding full bibliography for 4033613--4033615.cif.'
_cod_database_code               4033613
_shelx_shelxl_version_number     2017/1
_diffrn_oxdiff_ac3_digest_frames
;
017c9f51f5462b715488e7bea87936ec6000038fe24
;
_diffrn_oxdiff_ac3_digest_hkl
;
012a205b91d7c30bb565252bbfb6c33061d07a
;
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Ternary CH refined with riding coordinates:
 C007(H007), C008(H008)
2.b Secondary CH2 refined with riding coordinates:
 C009(H00A,H00B)
2.c Aromatic/amide H refined with riding coordinates:
 C00C(H00C), C00D(H00D), C00F(H00F), C00G(H00G), C00I(H00J), C00J(H00K),
 C00K(H00L), C00L(H00M)
2.d Idealised Me refined as rotating group:
 C00H(H00E,H00H,H00I)
;
_shelx_res_checksum              43225
_shelx_hkl_checksum              54865
_olex2_submission_original_sample_id 4-methoxy-6-nitro-2-phenylchromane
_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 1.319
_oxdiff_exptl_absorpt_empirical_full_min 0.755