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_4034591
_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         'C34 H27 N O2'
_chemical_formula_sum            'C34 H27 N O2'
_chemical_formula_weight         481.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.18 svn.r3501 for OlexSys, GUI svn.r5488)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.2452(3)
_cell_length_b                   17.0853(3)
_cell_length_c                   19.0868(3)
_cell_measurement_reflns_used    17513
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      71.8710
_cell_measurement_theta_min      3.5610
_cell_volume                     4971.52(15)
_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 0.992
_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    -71.00  10.00   0.50    0.24    --  -41.35 100.00  -9.00  162
  2  \w    -12.00  22.00   0.50    0.24    --  -41.35  26.00-135.00   68
  3  \w    -50.00 -23.00   0.50    0.24    --  -41.35  26.00-135.00   54
  4  \w     53.00  82.00   0.50    0.24    --   41.35 160.00-134.00   58
  5  \w     33.00  84.00   0.50    0.24    --   41.35  26.00-135.00  102
  6  \w     -3.00  31.00   0.50    0.24    --   41.35-117.00 -13.00   68
  7  \w     33.00  58.00   0.50    0.24    --   41.35-100.00-114.00   50
  8  \w    -18.00   8.00   0.50    0.24    --   41.35-100.00-114.00   52
  9  \w     33.00  60.00   0.50    0.24    --   41.35-117.00 -13.00   54
 10  \w     -7.00  18.00   0.50    0.24    --   41.35 -26.00  61.00   50
 11  \w    118.00 143.00   0.50    0.98    --  101.00 100.00  -9.00   50
 12  \w     70.00  96.00   0.50    0.98    --  101.00-117.00 -13.00   52
 13  \w    106.00 157.00   0.50    0.98    --  101.00  26.00-135.00  102
 14  \w     63.00  89.00   0.50    0.98    --  101.00 -26.00  61.00   52
 15  \w     92.00 118.00   0.50    0.98    --  101.00 117.00  73.00   52
 16  \w     34.00 110.00   0.50    0.98    --  101.00-100.00-114.00  152
 17  \w    -78.00 -45.00   0.50    0.24    --  -41.35 -26.00  61.00   66
 18  \w   -103.00 -27.00   0.50    0.24    --  -41.35 -54.00-120.00  152
 19  \w    -47.00 -22.00   0.50    0.24    --  -41.35 117.00  73.00   50
 20  \w     -9.00  38.00   0.50    0.24    --   41.35 -65.00  60.00   94
 21  \w     88.00 144.00   0.50    0.98    --  101.00  17.00 120.00  112
 22  \w    121.00 147.00   0.50    0.98    --  101.00 111.00 120.00   52
 23  \w     55.00  81.00   0.50    0.98    --  101.00-111.00-180.00   52
 24  \w     38.00 126.00   0.50    0.98    --  101.00 -77.00  30.00  176
 25  \w     93.00 157.00   0.50    0.98    --  101.00  17.00-180.00  128
 26  \w     38.00 110.00   0.50    0.98    --  101.00 -59.00 -90.00  144
 27  \w     41.00  92.00   0.50    0.98    --  101.00 -33.00-180.00  102
 28  \w     41.00  72.00   0.50    0.98    --  101.00-160.00-165.00   62
 29  \w     50.00  76.00   0.50    0.98    --  101.00 -26.00  61.00   52
 30  \w    123.00 155.00   0.50    0.98    --  101.00  17.00   0.00   64
 31  \w     48.00  91.00   0.50    0.98    --  101.00 -77.00-180.00   86
 32  \w     95.00 125.00   0.50    0.98    --  101.00 -77.00-180.00   60
 33  \w     70.00 106.00   0.50    0.98    --  101.00 -33.00-120.00   72
 34  \w     89.00 115.00   0.50    0.98    --  101.00  42.00  60.00   52
 35  \w    127.00 153.00   0.50    0.98    --  101.00  42.00  60.00   52
 36  \w     87.00 113.00   0.50    0.98    --  101.00  77.00  60.00   52
 37  \w    129.00 154.00   0.50    0.98    --  101.00  77.00  60.00   50
 38  \w     63.00  90.00   0.50    0.98    --  101.00-111.00 -30.00   54
;
_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      -0.0273931000
_diffrn_orient_matrix_UB_12      0.0398778000
_diffrn_orient_matrix_UB_13      -0.0690218000
_diffrn_orient_matrix_UB_21      0.0208026000
_diffrn_orient_matrix_UB_22      -0.0758095000
_diffrn_orient_matrix_UB_23      -0.0403494000
_diffrn_orient_matrix_UB_31      -0.0950294000
_diffrn_orient_matrix_UB_32      -0.0281482000
_diffrn_orient_matrix_UB_33      0.0110391000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0426
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            27282
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.041
_diffrn_reflns_theta_min         4.525
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.620
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40282
_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    1.287
_exptl_crystal_description       prism
_exptl_crystal_F_000             2032
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.239
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         4852
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0438P)^2^+2.2109P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0919
_refine_ls_wR_factor_ref         0.0935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4556
_reflns_number_total             4852
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00753_si_002.cif
_cod_data_source_block           Step-69
_cod_original_cell_volume        4971.51(16)
_cod_database_code               4034591
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C34 H27 N O2'
_shelx_estimated_absorpt_t_max   0.789
_shelx_estimated_absorpt_t_min   0.707
_reflns_odcompleteness_completeness 99.70
_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
2.a Ternary CH refined with riding coordinates:
 C5(H5), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C6(H6A,H6B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C21(H21), C37(H37), C27(H27), C25(H25), C36(H36), C31(H31),
 C23(H23), C33(H33), C35(H35), C34(H34), C30(H30), C29(H29), C15(H15), C28(H28),
  C22(H22), C12(H12), C14(H14), C13(H13)
;
_shelx_res_checksum              27178
_shelx_hkl_checksum              8081
_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 1.729
_oxdiff_exptl_absorpt_empirical_full_min 0.486