Synthesis of chromans and kinetic resolution of 2-aryl-3-nitro-2H-chromenes via the NHC-bound azolium homoenolate pathway
Bhattacharya, Aditya; mani Shukla, Pushpendra; Kumar Kaushik, Lalit; Maji, Biswajit; Organic Chemistry Frontiers 6 (2019) 3523–; doi:10.1039/C9QO00868C

data_1555101
_publ_section_title
;
 Synthesis of chromans and kinetic resolution of
 2-aryl-3-nitro-2H-chromenes via the NHC-bound azolium homoenolate pathway
;
_journal_issue                   20
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              3523
_journal_paper_doi               10.1039/C9QO00868C
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C25 H22 F N O5'
_chemical_formula_sum            'C25 H22 F N O5'
_chemical_formula_weight         435.43
_chemical_name_systematic        BM6
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2019-06-03 deposited with the CCDC.	2019-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9187(5)
_cell_length_b                   14.6101(9)
_cell_length_c                   16.5218(9)
_cell_measurement_reflns_used    3377
_cell_measurement_temperature    293
_cell_measurement_theta_max      21.1760
_cell_measurement_theta_min      3.6300
_cell_volume                     2152.8(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0309
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
  1 omega  -38.00   50.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8284   57.0000    0.0000 88

  2 omega   16.00   42.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8284   57.0000 -150.0000 26

  3 omega    1.00   85.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.9534   57.0000 -180.0000 84

  4 omega   38.00   73.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.9534  178.0000 -150.0000 35

  5 omega  -52.00   28.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.9534  -57.0000   30.0000 80

  6 omega   34.00   59.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.9534  -99.0000   60.0000 25

  7 omega  -20.00   59.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       16.9534  -99.0000  -90.0000 79

  8 omega  -25.00    9.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8284  -77.0000    0.0000 34

  9 omega  -57.00  -31.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8284  -77.0000  150.0000 26

 10 omega  -85.00  -34.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.8284  -57.0000  -90.0000 51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0110654000
_diffrn_orient_matrix_UB_12      0.0271643000
_diffrn_orient_matrix_UB_13      -0.0350414000
_diffrn_orient_matrix_UB_21      0.0216215000
_diffrn_orient_matrix_UB_22      0.0395612000
_diffrn_orient_matrix_UB_23      0.0220188000
_diffrn_orient_matrix_UB_31      0.0757142000
_diffrn_orient_matrix_UB_32      -0.0073678000
_diffrn_orient_matrix_UB_33      -0.0114384000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0800
_diffrn_reflns_av_unetI/netI     0.0670
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            18883
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.983
_diffrn_reflns_theta_max         24.983
_diffrn_reflns_theta_min         3.362
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.099
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69572
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_preparation       'ethyl acetate hexane'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 756 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.3(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     290
_refine_ls_number_reflns         3792
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0976
_refine_ls_R_factor_gt           0.0578
_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^)+(0.0530P)^2^+0.2120P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1502
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2492
_reflns_number_total             3792
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00868c2.cif
_cod_data_source_block           igntu007
_cod_database_code               1555101
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C100 H150 N10 O60 F10'
_reflns_odcompleteness_completeness 99.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C16(H16), C2(H2), C9(H9), C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C15(H15), C14(H14), C20(H20), C5(H5), C13(H13), C24(H24), C4(H4),
 C21(H21), C8(H8), C22(H22), C23(H23), C7(H7)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_shelx_res_checksum              94495
_shelx_hkl_checksum              26712
_olex2_submission_special_instructions 'No special instructions were received'