Zn(II)-catalyzed asymmetric [3 + 2] cycloaddition of acyclic enones with azomethine ylides.
Kumar, Sundaravel Vivek; Olusegun, Jeremiah; Guiry, Patrick J.; Organic & biomolecular chemistry 22 (2024) 7148–7153; doi:10.1039/d4ob00854e

data_7159983
_publ_section_title
;
 Zn(II)-catalyzed asymmetric [3 + 2] cycloaddition of acyclic enones with
 azomethine ylides.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7148
_journal_page_last               7153
_journal_paper_doi               10.1039/d4ob00854e
_journal_volume                  22
_journal_year                    2024
_chemical_absolute_configuration rm
_chemical_compound_source        synthesis
_chemical_formula_moiety         'C76.41 H60 N4 O2 Zn, 2(C Cl2), 2(C)'
_chemical_formula_sum            'C80.41 H60 Cl4 N4 O2 Zn'
_chemical_formula_weight         1321.37
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-10-05 deposited with the CCDC.	2024-06-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   14.39140(10)
_cell_length_b                   14.39140(10)
_cell_length_c                   27.12110(10)
_cell_measurement_reflns_used    52775
_cell_measurement_temperature    108(5)
_cell_measurement_theta_max      76.2910
_cell_measurement_theta_min      1.6270
_cell_volume                     4864.57(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      108(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3196
_diffrn_detector_type            Atlas
_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    -70.00  30.00   1.00    2.08    --  -42.20  55.00 -67.00  100
  2  \w     33.00 146.00   1.00    8.29    --  112.00 -82.00 161.00  113
  3  \w    103.00 178.00   1.00    8.29    --  112.00  80.00 106.00   75
  4  \w     34.00 145.00   1.00    8.29    --  112.00 -80.00 -16.00  111
  5  \w   -117.00 -18.00   1.00    2.08    --  -42.20 -37.00 150.00   99
  6  \w    -67.00  32.00   1.00    2.08    --  -42.20  37.00-150.00   99
  7  \w     27.00  96.00   1.00    2.08    --   42.20-125.00-150.00   69
  8  \w     14.00 114.00   1.00    2.08    --   42.20  55.00 -67.00  100
  9  \w     39.00 109.00   1.00    8.29    --  112.00-111.00 -90.00   70
 10  \w    104.00 178.00   1.00    8.29    --  112.00 111.00 -90.00   74
 11  \w     39.00 109.00   1.00    8.29    --  112.00-111.00 -30.00   70
 12  \w    103.00 178.00   1.00    8.29    --  112.00  77.00-150.00   75
 13  \w     83.00 178.00   1.00    8.29    --  112.00  61.00  30.00   95
 14  \w     29.00 107.00   1.00    8.29    --  112.00 -94.00 120.00   78
 15  \w     86.00 178.00   1.00    8.29    --  112.00  45.00-180.00   92
 16  \w     39.00 109.00   1.00    8.29    --  112.00-111.00  30.00   70
 17  \w     86.00 178.00   1.00    8.29    --  112.00  45.00  90.00   92
 18  \w     39.00 109.00   1.00    8.29    --  112.00-111.00  90.00   70
 19  \w     29.00 107.00   1.00    8.29    --  112.00 -94.00-180.00   78
 20  \w    103.00 178.00   1.00    8.29    --  112.00  77.00 150.00   75
 21  \w     86.00 178.00   1.00    8.29    --  112.00  45.00  60.00   92
 22  \w     39.00 138.00   1.00    8.29    --  112.00 -45.00  60.00   99
 23  \w     39.00 138.00   1.00    8.29    --  112.00 -45.00   0.00   99
 24  \w   -114.00 -14.00   1.00    2.08    --  -42.20 -57.00 -30.00  100
 25  \w   -114.00 -14.00   1.00    2.08    --  -42.20 -57.00  60.00  100
 26  \w      6.00  55.00   1.00    2.08    --   42.20 -99.00  30.00   49
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0794408000
_diffrn_orient_matrix_UB_12      0.0042147000
_diffrn_orient_matrix_UB_13      0.0392496000
_diffrn_orient_matrix_UB_21      0.0725476000
_diffrn_orient_matrix_UB_22      -0.0030226000
_diffrn_orient_matrix_UB_23      -0.0409985000
_diffrn_orient_matrix_UB_31      0.0609093000
_diffrn_orient_matrix_UB_32      0.1234576000
_diffrn_orient_matrix_UB_33      -0.0023355000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            66795
_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         76.417
_diffrn_reflns_theta_min         3.546
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.456
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.326
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.75a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent light colourless'
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_description       block
_exptl_crystal_F_000             2053
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Chloroform + diethyl ether'
_exptl_crystal_size_max          0.362
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.247
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.497
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 2916 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.002(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     457
_refine_ls_number_reflns         6788
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0354
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0617P)^2^+1.6999P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0977
_refine_ls_wR_factor_ref         0.0981
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                6727
_reflns_number_total             6788
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00854e2.cif
_cod_data_source_block           exp_1339_auto
_cod_depositor_comments          'Adding full bibliography for 7159983.cif.'
_cod_original_cell_volume        4864.56(7)
_cod_database_code               7159983
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C80H76Cl4N4O2Zn
_chemical_oxdiff_usercomment     V-464_VivekKumar_GuiryGroup
_shelx_estimated_absorpt_t_max   0.582
_shelx_estimated_absorpt_t_min   0.470
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid body (RIGU) restrains
 C1A_1, C3B_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2BB_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3A_1, C1B_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2BB_1, C2BA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2, Cl1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: Cl1(0.6) Cl2(0.4)
4.a Ternary CH refined with riding coordinates:
 C26(H26), C33(H33)
4.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C10(H10A,H10B), C9(H9A,H9B), C16(H16A,H16B), C17(H17A,H17B)
4.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C31(H31), C30(H30), C29(H29), C28(H28), C35(H35), C12(H12), C2(H2),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C8(H8), C7(H7), C5(H5),
 C4(H4)
;
_shelx_res_checksum              37722
_shelx_hkl_checksum              27803
_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 1.759
_oxdiff_exptl_absorpt_empirical_full_min 0.659