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_4034593
_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         'C30 H27 N O3'
_chemical_formula_sum            'C30 H27 N O3'
_chemical_formula_weight         449.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_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                 111.9520(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.4257(2)
_cell_length_b                   18.31540(10)
_cell_length_c                   16.5931(2)
_cell_measurement_reflns_used    33495
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.1200
_cell_measurement_theta_min      2.4090
_cell_volume                     4629.99(9)
_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 0.994
_diffrn_measured_fraction_theta_max 0.987
_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    -83.00 -16.00   0.50    0.44    --  -41.35 149.00-175.00  134
  2  \w    -75.00 -31.00   0.50    0.44    --  -41.35 -20.00   6.00   88
  3  \w   -110.00 -84.00   0.50    0.44    --  -41.35 -20.00   6.00   52
  4  \w    -44.00 -18.00   0.50    0.44    --  -41.35 106.00 -61.00   52
  5  \w     58.00  83.00   0.50    0.44    --   41.35  20.00 173.00   50
  6  \w     20.00  45.00   0.50    0.44    --   41.35-123.00 -59.00   50
  7  \w     31.00  56.00   0.50    0.44    --   41.35  20.00 173.00   50
  8  \w     -7.00  31.00   0.50    0.44    --   41.35 -20.00   6.00   76
  9  \w     12.00  37.00   0.50    0.44    --   41.35-106.00-160.00   50
 10  \w     75.00 109.00   0.50    1.78    --  101.00-123.00 -59.00   68
 11  \w     45.00 100.00   0.50    1.78    --  101.00-106.00-160.00  110
 12  \w    114.00 141.00   0.50    1.78    --  101.00 106.00 -61.00   54
 13  \w     97.00 127.00   0.50    1.78    --  101.00  20.00 173.00   60
 14  \w    117.00 153.00   0.50    1.78    --  101.00 123.00  20.00   72
 15  \w     54.00 109.00   0.50    1.78    --  101.00 -20.00   6.00  110
 16  \w    -36.00 -11.00   0.50    0.44    --  -41.35  20.00 173.00   50
 17  \w     46.00  72.00   0.50    0.44    --   41.35-149.00 137.00   52
 18  \w     46.00 107.00   0.50    0.44    --   41.35  32.00 -30.00  122
 19  \w     36.00  61.00   0.50    0.44    --   41.35 -65.00 150.00   50
 20  \w    -14.00  12.00   0.50    0.44    --   41.35 -65.00 150.00   52
 21  \w     80.00 108.00   0.50    1.78    --  101.00 -96.00 -30.00   56
 22  \w     32.00  64.00   0.50    1.78    --  101.00 -96.00 -30.00   64
 23  \w     37.00  78.00   0.50    1.78    --  101.00 -33.00 120.00   82
 24  \w    128.00 156.00   0.50    1.78    --  101.00  33.00 -60.00   56
 25  \w     81.00 132.00   0.50    1.78    --  101.00  96.00-150.00  102
 26  \w     87.00 126.00   0.50    1.78    --  101.00  59.00-150.00   78
 27  \w     37.00  93.00   0.50    1.78    --  101.00 -96.00 120.00  112
 28  \w    132.00 157.00   0.50    1.78    --  101.00  20.00 173.00   50
 29  \w    -20.00   7.00   0.50    0.44    --   41.35 -43.00 -90.00   54
 30  \w     63.00  90.00   0.50    0.44    --   41.35  32.00-150.00   54
 31  \w     96.00 156.00   0.50    1.78    --  101.00  77.00  90.00  120
 32  \w     42.00 105.00   0.50    1.78    --  101.00 -42.00 -30.00  126
 33  \w    102.00 146.00   0.50    1.78    --  101.00  42.00   0.00   88
 34  \w     39.00  70.00   0.50    1.78    --  101.00 -42.00-180.00   62
 35  \w     41.00  99.00   0.50    1.78    --  101.00 -77.00 -90.00  116
 36  \w     49.00  81.00   0.50    1.78    --  101.00 -68.00-180.00   64
 37  \w     93.00 119.00   0.50    1.78    --  101.00 -68.00-180.00   52
 38  \w     78.00 117.00   0.50    1.78    --  101.00 -59.00 -60.00   78
 39  \w     38.00  65.00   0.50    1.78    --  101.00 -59.00 -60.00   54
 40  \w     77.00 104.00   0.50    0.44    --   41.35-149.00 137.00   54
 41  \w    -56.00 -29.00   0.50    0.44    --  -41.35  77.00  60.00   54
 42  \w     18.00  45.00   0.50    0.44    --   41.35 -43.00 -60.00   54
 43  \w    114.00 140.00   0.50    1.78    --  101.00  96.00  60.00   52
 44  \w     74.00 115.00   0.50    1.78    --  101.00-117.00 -90.00   82
 45  \w     74.00 100.00   0.50    1.78    --  101.00 -96.00 150.00   52
 46  \w     38.00  66.00   0.50    1.78    --  101.00-117.00  60.00   56
 47  \w     81.00 115.00   0.50    1.78    --  101.00-117.00  60.00   68
 48  \w     64.00  91.00   0.50    1.78    --  101.00-117.00  90.00   54
 49  \w     91.00 117.00   0.50    1.78    --  101.00  42.00 -30.00   52
 50  \w     63.00  99.00   0.50    1.78    --  101.00 -42.00 -90.00   72
 51  \w    121.00 147.00   0.50    1.78    --  101.00 149.00-175.00   52
 52  \w    -60.00 -35.00   0.50    0.44    --  -41.35  11.00  90.00   50
 53  \w    -96.00 -70.00   0.50    0.44    --  -41.35 -77.00  30.00   52
 54  \w    -57.00 -28.00   0.50    0.44    --  -41.35 -77.00  30.00   58
 55  \w     -4.00  30.00   0.50    0.44    --  -41.35  11.00  90.00   68
 56  \w    -48.00 -21.00   0.50    0.44    --  -41.35  32.00   0.00   54
 57  \w    -20.00   6.00   0.50    0.44    --  -41.35  32.00   0.00   52
 58  \w     26.00  57.00   0.50    0.44    --   41.35 -77.00 120.00   62
 59  \w    -20.00  30.00   0.50    0.44    --   41.35 -43.00 -30.00  100
 60  \w     29.00  56.00   0.50    0.44    --   41.35  54.00-150.00   54
 61  \w    -15.00  18.00   0.50    0.44    --   41.35 -77.00 120.00   66
 62  \w     75.00 103.00   0.50    0.44    --   41.35  32.00  90.00   56
 63  \w     88.00 113.00   0.50    1.78    --  101.00  17.00 -30.00   50
 64  \w     94.00 128.00   0.50    1.78    --  101.00-145.00 -90.00   68
 65  \w     81.00 123.00   0.50    1.78    --  101.00  68.00   0.00   84
 66  \w     59.00 108.00   0.50    1.78    --  101.00-117.00 -30.00   98
 67  \w    127.00 153.00   0.50    1.78    --  101.00  25.00 120.00   52
 68  \w     78.00 106.00   0.50    1.78    --  101.00 -25.00 -90.00   56
 69  \w    121.00 147.00   0.50    1.78    --  101.00 145.00   0.00   52
 70  \w     72.00 115.00   0.50    1.78    --  101.00 145.00   0.00   86
 71  \w     43.00 116.00   0.50    1.78    --  101.00-117.00 120.00  146
 72  \w     96.00 122.00   0.50    1.78    --  101.00  25.00 120.00   52
 73  \w     82.00 115.00   0.50    1.78    --  101.00  96.00  60.00   66
 74  \w    132.00 157.00   0.50    1.78    --  101.00  96.00  60.00   50
 75  \w     40.00  66.00   0.50    1.78    --  101.00-145.00 -90.00   52
 76  \w    124.00 153.00   0.50    1.78    --  101.00  42.00-180.00   58
 77  \w    132.00 157.00   0.50    1.78    --  101.00  25.00   0.00   50
 78  \w     90.00 117.00   0.50    1.78    --  101.00  42.00-180.00   54
 79  \w     70.00 113.00   0.50    1.78    --  101.00-117.00   0.00   86
 80  \w     56.00  88.00   0.50    1.78    --  101.00 -96.00   0.00   64
 81  \w    127.00 153.00   0.50    1.78    --  101.00  17.00 -30.00   52
 82  \w     39.00 108.00   0.50    1.78    --  101.00 -59.00  90.00  138
 83  \w     33.00  74.00   0.50    1.78    --  101.00 -25.00 -90.00   82
;
_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      -0.0240741000
_diffrn_orient_matrix_UB_12      0.0000940000
_diffrn_orient_matrix_UB_13      0.0812555000
_diffrn_orient_matrix_UB_21      0.0947945000
_diffrn_orient_matrix_UB_22      -0.0220225000
_diffrn_orient_matrix_UB_23      0.0563867000
_diffrn_orient_matrix_UB_31      0.0257228000
_diffrn_orient_matrix_UB_32      0.0811898000
_diffrn_orient_matrix_UB_33      0.0152466000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            52607
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.312
_diffrn_reflns_theta_min         3.230
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.657
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80096
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       prism
_exptl_crystal_F_000             1904
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.434
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     655
_refine_ls_number_reflns         9037
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0416
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0509P)^2^+2.2044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1050
_refine_ls_wR_factor_ref         0.1071
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8385
_reflns_number_total             9037
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00753_si_005.cif
_cod_data_source_block           step-71
_cod_database_code               4034593
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C30 H27 N O3'
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.803
_reflns_odcompleteness_completeness 99.03
_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
2. Others
 Sof(H11A)=Sof(C12B)=Sof(H12B)=Sof(C8B")=Sof(H8B")=Sof(C9B")=Sof(H9B")=
 Sof(C1D)=Sof(H1D)=1-FVAR(1)
 Sof(H11B)=Sof(C10B)=Sof(H10B)=Sof(C1E)=Sof(H1E)=Sof(C9B)=Sof(H9B)=Sof(C8B)=
 Sof(H8B)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C1(H1), C6AB(H6AB), C6A(H6A), C1B(H1B)
3.b Secondary CH2 refined with riding coordinates:
 C6(H6B,H6C), C4(H4A,H4B), C5(H5A,H5B), C4B(H4BA,H4BB), C5B(H5BA,H5BB),
 C6B(H6BA,H6BB), C14(H14D,H14E), C13B(H13A,H13B)
3.c Aromatic/amide H refined with riding coordinates:
 C20B(H20B), C16(H16), C11(H11), C12(H12), C7'(H7'), C17(H17), C16B(H16B),
 C4'(H4'), C19(H19), C8(H8), C19B(H19B), C18(H18), C10(H10), C20(H20), C13(H13),
  C18B(H18B), C5'(H5'), C17B(H17B), C6'(H6'), C7'B(H7'B), C4'B(H4'B),
 C6'B(H6'B), C5'B(H5'B), C11B(H11A), C12B(H12B), C10B(H10B), C8B"(H8B"),
 C9B"(H9B"), C1D(H1D), C1E(H1E), C9B(H9B), C8B(H8B)
3.d Idealised Me refined as rotating group:
 C14B(H14A,H14B,H14C), C1C(H1CA,H1CB,H1CC)
;
_shelx_res_checksum              98703
_shelx_hkl_checksum              78204
_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 1.395
_oxdiff_exptl_absorpt_empirical_full_min 0.560