The first organocatalytic, ortho-regioselective inverse-electron-demand hetero-Diels-Alder reaction
Hejmanowska, Joanna; Jasiński, Marcin; Wojciechowski, Jakub; Mlostoń, Grzegorz; Albrecht, Lukasz; Chem. Commun.  (2017) –; doi:10.1039/C7CC06518C

data_7120717
_publ_section_title
;
 The first organocatalytic, ortho-regioselective inverse-electron-demand
 hetero-Diels-Alder reaction
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC06518C
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H23 F3 N4 O4 S'
_chemical_formula_sum            'C27 H23 F3 N4 O4 S'
_chemical_formula_weight         556.55
_chemical_name_systematic
E)-1-(2,4-Dinitrophenyl)-2-(((3S,4R)-3-methyl-4-phenyl-6-(4-(trifluoromethyl)phenyl)-3,4-dihydro-2H-thiopyran-3-yl)methylene)hydrazine
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-07-12
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.08.26 svn.r3337 for Rigaku Oxford Diffraction, GUI svn.r5221)
;
_audit_update_record
;
2017-07-12 deposited with the CCDC.
2017-09-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   6.72742(6)
_cell_length_b                   18.3659(2)
_cell_length_c                   51.8482(5)
_cell_measurement_reflns_used    118483
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.7870
_cell_measurement_theta_min      3.5120
_cell_volume                     6406.11(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.16b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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     86.00 170.00   0.50   12.00    --  105.75  77.00  60.00  168
  2  \w     91.00 176.00   0.50   12.00    --  105.75 125.00  60.00  170
  3  \w     91.00 176.00   0.50   12.00    --  105.75 125.00   0.00  170
  4  \w    100.00 178.00   0.50   12.00    --  105.75  19.00 -60.00  156
  5  \w    100.00 178.00   0.50   12.00    --  105.75  38.00-150.00  156
  6  \w    100.00 178.00   0.50   12.00    --  105.75  38.00   0.00  156
  7  \w    100.00 178.00   0.50   12.00    --  105.75  38.00 -60.00  156
  8  \w     93.00 176.00   0.50   12.00    --  105.75  57.00   0.00  166
  9  \w     57.00 114.00   0.50   12.00    --  105.75   0.00 150.00  114
 10  \w    -95.00 -14.00   0.50   12.00    --  -84.25 125.00-150.00  162
 11  \w     -5.00  73.00   0.50    3.00    --    0.00  19.00  30.00  156
 12  \w    -49.00   8.00   0.50    3.00    --    0.00   0.00  90.00  114
 13  \w    -49.00   8.00   0.50    3.00    --    0.00   0.00-150.00  114
 14  \w    -49.00   8.00   0.50    3.00    --    0.00   0.00  30.00  114
 15  \w     -5.00  73.00   0.50    3.00    --    0.00  19.00-150.00  156
 16  \w    -74.00   6.00   0.50    3.00    --    0.00 -38.00-150.00  160
 17  \w    -64.00  20.00   0.50    3.00    --    0.00 -77.00   0.00  168
 18  \w    -64.00  20.00   0.50    3.00    --    0.00 -77.00  60.00  168
 19  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00-150.00  168
 20  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00 -60.00  168
 21  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00-180.00  168
 22  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00  30.00  168
 23  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00-120.00  168
 24  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00 -30.00  168
 25  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00 120.00  168
 26  \w    -25.00  24.00   0.50    3.00    --    0.00 -85.00-106.00   98
 27  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00 150.00  168
 28  \w   -148.00 -64.00   0.50   12.00    --  -84.25 -77.00  60.00  168
 29  \w     38.00 126.00   0.50   12.00    --  105.75-136.00  10.00  176
 30  \w     36.00 121.00   0.50   12.00    --  105.75-125.00-120.00  170
 31  \w     38.00 111.00   0.50   12.00    --  105.75 -99.00 120.00  146
 32  \w     38.00 111.00   0.50   12.00    --  105.75 -99.00 -60.00  146
 33  \w     38.00 111.00   0.50   12.00    --  105.75 -99.00 -30.00  146
 34  \w     38.00 111.00   0.50   12.00    --  105.75 -99.00   0.00  146
 35  \w     38.00 111.00   0.50   12.00    --  105.75 -99.00  90.00  146
 36  \w     38.00 111.00   0.50   12.00    --  105.75 -99.00  30.00  146
 37  \w     32.00  71.00   0.50   12.00    --  105.75 -38.00-150.00   78
 38  \w     36.00  96.00   0.50   12.00    --  105.75 -57.00  30.00  120
 39  \w     33.00 111.00   0.50   12.00    --  105.75 -19.00 -30.00  156
 40  \w     36.00  96.00   0.50   12.00    --  105.75 -57.00  90.00  120
 41  \w     42.00 126.00   0.50   12.00    --  105.75 -77.00 -60.00  168
 42  \w     32.00  71.00   0.50   12.00    --  105.75 -38.00  30.00   78
 43  \w     36.00  96.00   0.50   12.00    --  105.75 -57.00 -30.00  120
 44  \w     42.00 126.00   0.50   12.00    --  105.75 -77.00 -30.00  168
 45  \w     36.00  96.00   0.50   12.00    --  105.75 -57.00   0.00  120
 46  \w     36.00  96.00   0.50   12.00    --  105.75 -57.00  60.00  120
 47  \w     33.00 111.00   0.50   12.00    --  105.75 -19.00 -60.00  156
 48  \w     36.00  96.00   0.50   12.00    --  105.75 -57.00 120.00  120
 49  \w     93.00 176.00   0.50   12.00    --  105.75  57.00  30.00  166
 50  \w     57.00 114.00   0.50   12.00    --  105.75   0.00 -90.00  114
 51  \w     86.00 170.00   0.50   12.00    --  105.75  77.00-120.00  168
 52  \w    100.00 178.00   0.50   12.00    --  105.75  19.00 150.00  156
 53  \w    100.00 178.00   0.50   12.00    --  105.75  19.00-150.00  156
 54  \w     86.00 170.00   0.50   12.00    --  105.75  77.00 -60.00  168
 55  \w    100.00 178.00   0.50   12.00    --  105.75  19.00 -90.00  156
 56  \w    100.00 178.00   0.50   12.00    --  105.75  19.00-180.00  156
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1673028000
_diffrn_orient_matrix_UB_12      0.0511841000
_diffrn_orient_matrix_UB_13      -0.0091276000
_diffrn_orient_matrix_UB_21      0.1563655000
_diffrn_orient_matrix_UB_22      -0.0540530000
_diffrn_orient_matrix_UB_23      0.0102366000
_diffrn_orient_matrix_UB_31      0.0028281000
_diffrn_orient_matrix_UB_32      -0.0386778000
_diffrn_orient_matrix_UB_33      -0.0263529000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0655
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       62
_diffrn_reflns_limit_l_min       -66
_diffrn_reflns_number            208346
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.954
_diffrn_reflns_theta_min         3.410
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.351
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71501
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.16b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_description       plate
_exptl_crystal_F_000             2304
_exptl_crystal_size_max          0.211
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.037
_refine_diff_density_max         0.264
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 5497 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     713
_refine_ls_number_reflns         13828
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0366
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0572P)^2^+1.7252P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0973
_refine_ls_wR_factor_ref         0.0986
_reflns_Friedel_coverage         0.772
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                13203
_reflns_number_total             13828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc06518c2.cif
_cod_data_source_block           la_jh_251_cf3
_cod_original_cell_volume        6406.12(11)
_cod_database_code               7120717
_chemical_oxdiff_formula         'C20 H30 S1 F3 O4 N2'
_reflns_odcompleteness_completeness 99.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     79.66
_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:
 C3B(H3B), C3A(H3A)
2.b Secondary CH2 refined with riding coordinates:
 C1B(H1BA,H1BB), C20B(H20A,H20B), C1A(H1AA,H1AB), C20A(H20C,H20D)
2.c Aromatic/amide H refined with riding coordinates:
 C4B(H4B), C8B(H8B), C9B(H9B), C10B(H10B), C11B(H11B), C12B(H12B), C14B(H14B),
 C15B(H15B), C18B(H18B), C19B(H19B), C21B(H21B), C24B(H24B), C26B(H26B),
 C27B(H27B), C4A(H4A), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A),
 C14A(H14A), C15A(H15A), C18A(H18A), C19A(H19A), C21A(H21A), C24A(H24A),
 C26A(H26A), C27A(H27A)
2.d Idealised Me refined as rotating group:
 C6B(H6BA,H6BB,H6BC), C6A(H6AA,H6AB,H6AC)
;
_shelx_res_checksum              25779
_shelx_fab_checksum              44576
_shelx_shelxl_version_number     2014/7
_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 1.597
_oxdiff_exptl_absorpt_empirical_full_min 0.714