Periselectivity in the aza-Diels-Alder cycloaddition between α-oxoketenes and N-(5-pyrazolyl)imines: a combined experimental and theoretical study.
Castillo, Juan-Carlos; Castro-Agudelo, Brian; Gálvez, Jaime; Carissan, Yannick; Rodríguez, Jean; Coquerel, Yoann; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00767

data_4038411
_publ_section_title
;
 Periselectivity in the aza-Diels-Alder cycloaddition between
 \a-oxoketenes and N-(5-pyrazolyl)imines: a combined experimental and
 theoretical study.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00767
_journal_year                    2020
_chemical_formula_moiety         'C8 H10 O3, 0.25(H2 O)'
_chemical_formula_sum            'C8 H10.5 O3.25'
_chemical_formula_weight         156.16
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2020-02-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                99.977(2)
_cell_angle_beta                 101.184(2)
_cell_angle_gamma                90.391(2)
_cell_formula_units_Z            8
_cell_length_a                   9.7851(2)
_cell_length_b                   10.0054(3)
_cell_length_c                   17.1038(4)
_cell_measurement_reflns_used    12756
_cell_measurement_temperature    295
_cell_measurement_theta_max      70.9080
_cell_measurement_theta_min      4.5740
_cell_volume                     1616.47(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      295
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.986
_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     -9.00  16.00   1.00    1.00    --   34.00 102.00 -80.78   25
  2  \w     -1.00  24.00   1.00    1.00    --   38.00  95.00 173.18   25
  3  \w    -67.00  13.00   1.00    1.00    --  -41.07  57.00 120.00   80
  4  \w   -111.00 -13.00   1.00    1.00    --  -41.07 -57.00  60.00   98
  5  \w    -60.00 -17.00   1.00    1.00    --  -41.07 -38.00 150.00   43
  6  \w   -113.00 -65.00   1.00    1.00    --  -41.07 -38.00 150.00   48
  7  \w   -109.00 -17.00   1.00    1.00    --  -41.07 -57.00 -60.00   92
  8  \w     23.00  96.00   1.00    1.00    --   41.07-125.00 -30.00   73
  9  \w      6.00  31.00   1.00    1.00    --   42.00  88.00  79.64   25
 10  \w     12.00  37.00   1.00    1.00    --   46.00  83.00 -67.72   25
 11  \w     18.00  44.00   1.00    1.00    --   50.00  82.00-173.54   26
 12  \w     17.00  42.00   1.00    1.00    --   50.00  78.00  96.19   25
 13  \w     16.00  41.00   1.00    1.00    --   50.00  81.00 -16.39   25
 14  \w     22.00  48.00   1.00    1.00    --   54.00  74.00-102.70   26
 15  \w     29.00  55.00   1.00    1.00    --   62.00  77.00 121.89   26
 16  \w     34.00  60.00   1.00    1.00    --   66.00  75.00 -57.04   26
 17  \w    102.00 128.00   1.00    1.00    --   66.00  77.00  70.50   26
 18  \w     33.00  59.00   1.00    1.00    --   66.00  77.00   5.75   26
 19  \w    108.00 142.00   1.00    1.00    --   66.00  77.00   5.75   34
 20  \w    111.00 140.00   1.00    1.00    --   66.00  77.00-179.32   29
 21  \w     34.00  60.00   1.00    1.00    --   66.00  77.00  31.03   26
 22  \w     35.00  63.00   1.00    1.00    --   66.00  77.00-179.32   28
 23  \w     34.00  62.00   1.00    1.00    --   66.00  77.00  70.50   28
 24  \w     99.00 146.00   1.00    1.00    --   70.00  76.00 -44.36   47
 25  \w     38.00  75.00   1.00    1.00    --   70.00  76.00 -44.36   37
 26  \w     38.00  77.00   1.00    1.00    --   70.00  76.00-108.13   39
 27  \w     38.00  75.00   1.00    1.00    --   70.00  76.00 135.21   37
 28  \w     83.00 137.00   1.00    1.00    --   70.00  76.00 135.21   54
 29  \w     41.00  67.00   1.00    1.00    --   70.00  76.00  45.36   26
 30  \w     41.00  71.00   1.00    5.00    --   74.00  77.00-152.51   30
 31  \w     91.00 116.00   1.00    5.00    --  101.41-125.00  90.00   25
 32  \w    103.00 145.00   1.00    5.00    --  101.41  77.00 -60.00   42
 33  \w     41.00 105.00   1.00    5.00    --  101.41-125.00-150.00   64
 34  \w     69.00  95.00   1.00    5.00    --  101.41  77.00 -60.00   26
 35  \w     98.00 159.00   1.00    5.00    --  101.41  77.00  90.00   61
 36  \w     71.00  97.00   1.00    5.00    --  101.41  77.00  90.00   26
 37  \w     70.00 149.00   1.00    5.00    --  101.41  77.00  30.00   79
 38  \w     69.00 154.00   1.00    5.00    --  101.41  77.00 120.00   85
 39  \w     69.00  95.00   1.00    5.00    --  101.41  77.00 -90.00   26
 40  \w     69.00 163.00   1.00    5.00    --  101.41  77.00-120.00   94
 41  \w     84.00 114.00   1.00    5.00    --  101.41-125.00 -30.00   30
 42  \w    100.00 149.00   1.00    5.00    --  101.41  77.00  60.00   49
 43  \w     69.00  95.00   1.00    5.00    --  101.41  77.00  60.00   26
 44  \w     98.00 178.00   1.00    5.00    --  101.41  77.00 -90.00   80
 45  \w    118.00 152.00   1.00    5.00    --  101.41  77.00 150.00   34
 46  \w     69.00 113.00   1.00    5.00    --  101.41  77.00 150.00   44
 47  \w     69.00 177.00   1.00    5.00    --  101.41  77.00   0.00  108
 48  \w     32.00 130.00   1.00    5.00    --  101.41 -61.00-120.00   98
 49  \w    100.00 173.00   1.00    5.00    --  101.41  77.00 -30.00   73
 50  \w     69.00  95.00   1.00    5.00    --  101.41  77.00 -30.00   26
 51  \w     44.00 132.00   1.00    5.00    --  101.41 -77.00   0.00   88
 52  \w     65.00  96.00   1.00    5.00    --  101.41-109.00-128.00   31
 53  \w     72.00 174.00   1.00    5.00    --  101.41  77.00-180.00  102
 54  \w     69.00 165.00   1.00    5.00    --  101.41  77.00-150.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0531073000
_diffrn_orient_matrix_UB_12      -0.1361510000
_diffrn_orient_matrix_UB_13      0.0159032000
_diffrn_orient_matrix_UB_21      -0.0738944000
_diffrn_orient_matrix_UB_22      -0.0372933000
_diffrn_orient_matrix_UB_23      -0.0894771000
_diffrn_orient_matrix_UB_31      0.1323656000
_diffrn_orient_matrix_UB_32      -0.0674999000
_diffrn_orient_matrix_UB_33      -0.0211349000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            26293
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.025
_diffrn_reflns_theta_min         4.491
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.848
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77752
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.304
_exptl_crystal_description       needle
_exptl_crystal_F_000             676
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.165
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     425
_refine_ls_number_reflns         6134
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0492
_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^)+(0.0921P)^2^+0.2391P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1466
_refine_ls_wR_factor_ref         0.1554
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5239
_reflns_number_total             6134
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00767_si_001.cif
_cod_data_source_block           bca180
_cod_depositor_comments
;

2025-07-29
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '4(C8 H10 O3), H2 O'
_cod_original_formula_sum        'C32 H42 O13'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     634.65
_cod_database_code               4038411
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         'c10 h12 o4'
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.739
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2.a Free rotating group:
 O13(H13A,H13B)
2.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3), O6(H6), O9(H9), O12(H12)
;
_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 1.436
_oxdiff_exptl_absorpt_empirical_full_min 0.711