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_7247300
_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         'C23 H21 N O'
_chemical_formula_sum            'C23 H21 N O'
_chemical_formula_weight         327.41
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-12-06
_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                86.525(5)
_cell_angle_beta                 87.942(5)
_cell_angle_gamma                87.181(5)
_cell_formula_units_Z            4
_cell_length_a                   5.8318(4)
_cell_length_b                   11.6046(8)
_cell_length_c                   26.5835(15)
_cell_measurement_reflns_used    3813
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      73.5270
_cell_measurement_theta_min      3.2910
_cell_volume                     1792.6(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      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.959
_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    -26.00  31.00   1.00    1.21    --  -40.73  57.00  90.00   57
  2  \w    -51.00  -7.00   1.00    1.21    --  -40.73 125.00 -30.00   44
  3  \w    -67.00 -27.00   1.00    1.21    --  -40.73  57.00-150.00   40
  4  \w    -63.00  31.00   1.00    1.21    --  -40.73  38.00-120.00   94
  5  \w    -73.00  35.00   1.00    1.21    --  -40.73  77.00 -60.00  108
  6  \w    -87.00 -54.00   1.00    1.21    --  -40.73 125.00 -30.00   33
  7  \w     27.00 105.00   1.00    1.20    --  108.20 -94.00 150.00   78
  8  \w     84.00 111.00   1.00    1.20    --  108.20-125.00 120.00   27
  9  \w     47.00 132.00   1.00    1.20    --  108.20 -45.00 150.00   85
 10  \w     88.00 134.00   1.00    1.20    --  108.20  45.00 120.00   46
 11  \w     98.00 160.00   1.00    1.20    --  108.20  61.00  30.00   62
 12  \w     84.00 147.00   1.00    1.20    --  108.20  30.00 -30.00   63
 13  \w     82.00 165.00   1.00    1.20    --  108.20  45.00   0.00   83
 14  \w     94.00 120.00   1.00    1.20    --  108.20 125.00-150.00   26
 15  \w     49.00  95.00   1.00    1.20    --  108.20 -30.00  90.00   46
 16  \w     42.00 133.00   1.00    1.20    --  108.20 -61.00 -30.00   91
 17  \w     62.00 120.00   1.00    1.20    --  108.20-125.00 -30.00   58
 18  \w     37.00  63.00   1.00    1.20    --  108.20-125.00 120.00   26
 19  \w     27.00  96.00   1.00    1.20    --  108.20 -94.00 -30.00   69
;
_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      0.1273386000
_diffrn_orient_matrix_UB_12      0.0119199000
_diffrn_orient_matrix_UB_13      -0.0517010000
_diffrn_orient_matrix_UB_21      0.1038033000
_diffrn_orient_matrix_UB_22      -0.1240904000
_diffrn_orient_matrix_UB_23      0.0082006000
_diffrn_orient_matrix_UB_31      -0.2074578000
_diffrn_orient_matrix_UB_32      -0.0467708000
_diffrn_orient_matrix_UB_33      -0.0251842000
_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  0.0461
_diffrn_reflns_av_unetI/netI     0.0583
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            12192
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.215
_diffrn_reflns_theta_min         3.333
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.571
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48948
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.400
_refine_diff_density_min         -0.280
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         7010
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0868
_refine_ls_R_factor_gt           0.0614
_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^)+(0.0667P)^2^+0.8998P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1720
_refine_ls_wR_factor_ref         0.1892
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5020
_reflns_number_total             7010
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc02073h2.cif
_cod_data_source_block           lyl1101
_cod_depositor_comments
'Adding full bibliography for 7247297--7247301.cif.'
_cod_database_code               7247300
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.924
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C30(H30A,H30B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2A), C9(H9), C18(H18), C21(H21), C22(H22), C12(H12), C16(H16),
 C19(H19), C5(H5), C1(H1A), C3(H3), C28(H28), C24(H24), C32(H32), C2(H2),
 C25(H25), C4(H4), C26(H26), C15(H15), C27(H27), C13(H13), C35(H35), C39(H39),
 C45(H45), C14(H14), C44(H44), C36(H36), C37(H37), C41(H41), C42(H42), C38(H38)
2.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              94444
_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 1.647
_oxdiff_exptl_absorpt_empirical_full_min 0.467