Stereo- and Regioselective 1,3-Dipolar Cycloaddition of the Stable Ninhydrin-Derived Azomethine Ylide to Cyclopropenes: Trapping of Unstable Cyclopropene Dipolarophiles.
Filatov, Alexander S.; Wang, Siqi; Khoroshilova, Olesya V.; Lozovskiy, Stanislav V.; Larina, Anna G.; Boitsov, Vitali M.; Stepakov, Alexander V.; The Journal of organic chemistry 84 (2019) 7017–7036; doi:10.1021/acs.joc.9b00753

data_4034594
_publ_section_title
;
 Stereo- and Regioselective 1,3-Dipolar Cycloaddition of the Stable
 Ninhydrin-Derived Azomethine Ylide to Cyclopropenes: Trapping of Unstable
 Cyclopropene Dipolarophiles.
;
_journal_issue                   11
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7017
_journal_page_last               7036
_journal_paper_doi               10.1021/acs.joc.9b00753
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C25 H23 N O4'
_chemical_formula_sum            'C25 H23 N O4'
_chemical_formula_weight         401.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.360(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9200(4)
_cell_length_b                   10.2331(3)
_cell_length_c                   15.3199(4)
_cell_measurement_reflns_used    13869
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.7860
_cell_measurement_theta_min      2.8460
_cell_volume                     1998.50(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -51.00 -18.00   0.50    0.20    --  -41.22 125.00 -14.00   66
  2  \w     11.00  37.00   0.50    0.20    --   41.22-125.00 -92.00   52
  3  \w     39.00  65.00   0.50    0.20    --   41.22-125.00 -92.00   52
  4  \w     15.00  86.00   0.50    0.20    --   41.22-145.00 100.00  142
  5  \w     76.00 154.00   0.50    0.22    --  101.00 125.00 -14.00  156
  6  \w     77.00 130.00   0.50    0.22    --  101.00-145.00 100.00  106
  7  \w     62.00 127.00   0.50    0.22    --  101.00 145.00 152.00  130
  8  \w     78.00 115.00   0.50    0.22    --  101.00-125.00 -92.00   74
  9  \w     -2.00  28.00   0.50    0.20    --  -41.22  21.00-150.00   60
 10  \w    -57.00  18.00   0.50    0.20    --  -41.22  54.00   0.00  150
 11  \w   -104.00 -32.00   0.50    0.20    --  -41.22 -43.00  60.00  144
 12  \w    -49.00  -7.00   0.50    0.20    --  -41.22  21.00-150.00   84
 13  \w    -56.00 -11.00   0.50    0.20    --  -41.22  54.00 -60.00   90
 14  \w   -100.00 -73.00   0.50    0.20    --  -41.22 145.00 152.00   54
 15  \w     27.00  57.00   0.50    0.20    --   41.22-104.00   0.00   60
 16  \w     71.00 104.00   0.50    0.20    --   41.22  43.00-150.00   66
 17  \w     25.00  50.00   0.50    0.20    --   41.22 -32.00-180.00   50
 18  \w    -12.00  20.00   0.50    0.20    --   41.22-104.00   0.00   64
 19  \w    -22.00   5.00   0.50    0.20    --   41.22 -32.00-180.00   54
 20  \w    -12.00  14.00   0.50    0.20    --   41.22 -32.00-120.00   52
 21  \w     49.00  80.00   0.50    0.20    --   41.22  32.00-180.00   62
 22  \w     30.00  55.00   0.50    0.20    --   41.22  43.00-150.00   50
 23  \w     72.00 114.00   0.50    0.22    --  101.00-111.00 -60.00   84
 24  \w     81.00 114.00   0.50    0.22    --  101.00 -17.00   0.00   66
 25  \w     35.00  61.00   0.50    0.22    --  101.00-111.00 -60.00   52
 26  \w    124.00 155.00   0.50    0.22    --  101.00  68.00 150.00   62
 27  \w     80.00 156.00   0.50    0.22    --  101.00 111.00 -30.00  152
 28  \w     81.00 156.00   0.50    0.22    --  101.00 111.00-150.00  150
 29  \w     89.00 114.00   0.50    0.22    --  101.00-111.00  60.00   50
 30  \w     35.00  61.00   0.50    0.22    --  101.00-111.00  60.00   52
 31  \w     91.00 128.00   0.50    0.22    --  101.00 -87.00  90.00   74
 32  \w     42.00 122.00   0.50    0.22    --  101.00 -68.00  90.00  160
 33  \w     90.00 134.00   0.50    0.22    --  101.00  17.00 -30.00   88
 34  \w     34.00  59.00   0.50    0.22    --  101.00 -17.00   0.00   50
 35  \w     43.00  69.00   0.50    0.22    --  101.00 -87.00  90.00   52
 36  \w     82.00 153.00   0.50    0.22    --  101.00  93.00 -60.00  142
 37  \w     72.00  98.00   0.50    0.22    --  101.00 -59.00 -60.00   52
 38  \w     61.00  86.00   0.50    0.22    --  101.00-111.00-120.00   50
 39  \w     40.00 105.00   0.50    0.22    --  101.00 -87.00  60.00  130
 40  \w     53.00 103.00   0.50    0.22    --  101.00 -33.00-150.00  100
 41  \w     38.00  88.00   0.50    0.20    --   41.22  77.00 -90.00  100
 42  \w    -56.00 -21.00   0.50    0.20    --  -41.22 -65.00-120.00   70
 43  \w    -84.00 -37.00   0.50    0.20    --  -41.22 -65.00 -30.00   94
 44  \w    -97.00 -69.00   0.50    0.20    --  -41.22 -65.00-120.00   56
 45  \w     33.00  60.00   0.50    0.20    --   41.22  32.00-180.00   54
 46  \w     23.00  49.00   0.50    0.20    --   41.22 -32.00 120.00   52
 47  \w     27.00  59.00   0.50    0.20    --   41.22 -65.00  60.00   64
 48  \w    -15.00  51.00   0.50    0.20    --   41.22 -43.00  30.00  132
 49  \w     41.00  91.00   0.50    0.22    --  101.00 -25.00-180.00  100
 50  \w     39.00 117.00   0.50    0.22    --  101.00 -50.00  60.00  156
 51  \w    107.00 142.00   0.50    0.22    --  101.00  93.00  30.00   70
 52  \w    121.00 157.00   0.50    0.22    --  101.00 111.00 120.00   72
 53  \w    123.00 148.00   0.50    0.22    --  101.00  33.00  60.00   50
 54  \w     89.00 115.00   0.50    0.22    --  101.00-111.00  60.00   52
 55  \w     98.00 123.00   0.50    0.22    --  101.00 -68.00 -60.00   50
 56  \w     39.00  89.00   0.50    0.22    --  101.00 -68.00 -60.00  100
 57  \w     85.00 110.00   0.50    0.22    --  101.00 -33.00 -90.00   50
 58  \w    120.00 155.00   0.50    0.22    --  101.00  50.00  30.00   70
 59  \w     86.00 117.00   0.50    0.22    --  101.00  50.00  30.00   62
 60  \w     39.00  84.00   0.50    0.22    --  101.00 -87.00-120.00   90
 61  \w     48.00 108.00   0.50    0.22    --  101.00 -93.00 -60.00  120
 62  \w     72.00 118.00   0.50    0.22    --  101.00 133.00-150.00   92
 63  \w     96.00 121.00   0.50    0.22    --  101.00  33.00 -30.00   50
 64  \w     88.00 114.00   0.50    0.22    --  101.00 111.00-180.00   52
 65  \w     93.00 133.00   0.50    0.22    --  101.00  25.00-180.00   80
 66  \w     74.00 115.00   0.50    0.22    --  101.00-111.00 150.00   82
 67  \w     36.00  72.00   0.50    0.22    --  101.00 -33.00 -90.00   72
 68  \w     38.00  82.00   0.50    0.22    --  101.00 -68.00-120.00   88
 69  \w     92.00 156.00   0.50    0.22    --  101.00  25.00 150.00  128
 70  \w     27.00  52.00   0.50    0.22    --  101.00  -8.00  -8.00   50
 71  \w    -50.00 -24.00   0.50    0.20    --  -41.22  54.00-150.00   52
 72  \w    -58.00  -6.00   0.50    0.20    --  -41.22  54.00-120.00  104
 73  \w     38.00  65.00   0.50    0.22    --  101.00 -33.00   0.00   54
 74  \w     84.00 134.00   0.50    0.22    --  101.00  59.00  90.00  100
 75  \w     38.00  74.00   0.50    0.22    --  101.00-133.00-120.00   72
 76  \w     98.00 147.00   0.50    0.22    --  101.00  59.00 120.00   98
 77  \w    101.00 127.00   0.50    0.22    --  101.00  33.00  30.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0969070000
_diffrn_orient_matrix_UB_12      0.0885426000
_diffrn_orient_matrix_UB_13      0.0025098000
_diffrn_orient_matrix_UB_21      0.0715612000
_diffrn_orient_matrix_UB_22      -0.1213512000
_diffrn_orient_matrix_UB_23      0.0106082000
_diffrn_orient_matrix_UB_31      -0.0098826000
_diffrn_orient_matrix_UB_32      -0.0105170000
_diffrn_orient_matrix_UB_33      -0.1012863000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0438
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24262
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.935
_diffrn_reflns_theta_min         3.467
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.731
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67848
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       prism
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.551
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         3915
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0464
_refine_ls_R_factor_gt           0.0435
_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^)+(0.0487P)^2^+1.3526P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1081
_refine_ls_wR_factor_ref         0.1101
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3585
_reflns_number_total             3915
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00753_si_004.cif
_cod_data_source_block           step-72
_cod_original_cell_volume        1998.50(11)
_cod_database_code               4034594
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C25 H23 N O4'
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.800
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.55
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C4(H4)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C8(H8A,H8B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C21(H21), C12(H12), C25(H25), C22(H22), C13(H13), C14(H14), C24(H24)
2.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C26(H26A,H26B,H26C)
2.e Idealised tetrahedral OH refined as rotating group:
 O28(H28)
;
_shelx_res_checksum              46841
_shelx_hkl_checksum              921
_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 1.433
_oxdiff_exptl_absorpt_empirical_full_min 0.610