Green and effective synthesis of multisubstituted α-pyrones via K2CO3 catalyzed formal insertion of ketenimines into C(CO)–C bonds of 1,3-diketones
Luo, Jian; Zhong, Ai-Qing; Qiu, Jia-Hao; Liu, Xiong-Wei; Tian, You-Ping; Zhang, Bao-Hua; Chen, Guo-Shu; Shu, Wei; Liu, Yun-Lin; Green Chemistry 25 (2023) 8057–8067; doi:10.1039/D3GC02073H

data_7247298
_publ_section_title
;
 Green and effective synthesis of multisubstituted \a-pyrones via K2CO3
 catalyzed formal insertion of ketenimines into C(CO)--C bonds of
 1,3-diketones
;
_journal_issue                   20
_journal_name_full               'Green Chemistry'
_journal_page_first              8057
_journal_page_last               8067
_journal_paper_doi               10.1039/D3GC02073H
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety         'C35 H30 Cl N O6'
_chemical_formula_sum            'C35 H30 Cl N O6'
_chemical_formula_weight         596.05
_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             2023-02-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-28 deposited with the CCDC.	2023-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.050(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4332(5)
_cell_length_b                   10.0121(4)
_cell_length_c                   27.9684(13)
_cell_measurement_reflns_used    3878
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.3600
_cell_measurement_theta_min      3.1610
_cell_volume                     2892.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.971
_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      4.00  44.00   1.00    1.00    --   40.73 -99.00 -60.00   40
  2  \w     48.00 122.00   1.00    1.00    --  107.58-125.00  60.00   74
  3  \w     40.00 106.00   1.00    1.00    --  107.58 -30.00   0.00   66
  4  \w     83.00 178.00   1.00    1.00    --  107.58  45.00 -30.00   95
  5  \w     35.00 131.00   1.00    1.00    --  107.58 -61.00-180.00   96
  6  \w     32.00 110.00   1.00    1.00    --  107.58 -95.00 150.00   78
  7  \w    -68.00 -41.00   1.00    1.00    --  -40.73  57.00 150.00   27
  8  \w   -115.00  -8.00   1.00    1.00    --  -40.73 -77.00   0.00  107
  9  \w   -114.00 -38.00   1.00    1.00    --  -40.73 -38.00-150.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0395472000
_diffrn_orient_matrix_UB_12      0.0507148000
_diffrn_orient_matrix_UB_13      0.0520107000
_diffrn_orient_matrix_UB_21      0.1217215000
_diffrn_orient_matrix_UB_22      0.0650993000
_diffrn_orient_matrix_UB_23      -0.0153106000
_diffrn_orient_matrix_UB_31      -0.0763208000
_diffrn_orient_matrix_UB_32      0.1298458000
_diffrn_orient_matrix_UB_33      -0.0126358000
_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  0.0409
_diffrn_reflns_av_unetI/netI     0.0602
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            10780
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.732
_diffrn_reflns_theta_min         3.192
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.577
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81832
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.061
_refine_ls_extinction_coef       0.00152(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         5666
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0699P)^2^+0.1876P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1325
_refine_ls_wR_factor_ref         0.1478
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4326
_reflns_number_total             5666
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc02073h2.cif
_cod_data_source_block           1207-02
_cod_depositor_comments
'Adding full bibliography for 7247297--7247301.cif.'
_cod_database_code               7247298
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.846
_shelx_estimated_absorpt_t_min   0.821
_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.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C34(H34), C31(H31), C19(H19), C30(H30), C33(H33), C28(H28), C15(H15), C7(H7),
 C6(H6), C3(H3), C24(H24), C11(H11), C4(H4), C25(H25), C27(H27), C26(H26),
 C12(H12)
2.c Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C17(H17A,H17B,H17C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              41018
_olex2_date_sample_data_collection 2020-12-11
_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 1.681
_oxdiff_exptl_absorpt_empirical_full_min 0.612