Base-promoted cascade annulation and annulation/carboxylation of α-enolizable phosphoryl substituted ynones and isatins with CO<sub>2</sub>.
Savoskin, Alexander E.; Efremov, Andrey N.; Murashkina, Arina V.; Gontcharenko, Victoriya E.; Bogdanov, Andrei V.; Mitrofanov, Alexander Yu; Beletskaya, Irina P.; Chemical communications (Cambridge, England) 61 (2025) 16230–16233; doi:10.1039/d5cc04158a

data_7134958
_publ_section_title
;
 Base-promoted cascade annulation and annulation/carboxylation of
 &#x3b1;-enolizable phosphoryl substituted ynones and isatins with
 CO<sub>2</sub>.
;
_journal_issue                   83
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              16230
_journal_page_last               16233
_journal_paper_doi               10.1039/d5cc04158a
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H23 Br N O6 P'
_chemical_formula_sum            'C19 H23 Br N O6 P'
_chemical_formula_weight         472.26
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-19
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-07-14 deposited with the CCDC.	2025-09-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.3187(6)
_cell_length_b                   10.3187(6)
_cell_length_c                   38.654(3)
_cell_measurement_reflns_used    5003
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      24.20
_cell_measurement_theta_min      2.23
_cell_volume                     4115.7(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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_temperature      100.00
_diffrn_detector                 'Photon III detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'Bruker D8 Quest'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1699
_diffrn_reflns_av_unetI/netI     0.1230
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            42384
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.582
_diffrn_reflns_theta_min         2.043
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.9
_diffrn_source_power             0.045
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.110
_exptl_absorpt_correction_T_max  0.6478
_exptl_absorpt_correction_T_min  0.5017
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1647 before and 0.0961 after correction.
The Ratio of minimum to maximum transmission is 0.7745.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.524
_exptl_crystal_description       block
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          0.074
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.051
_refine_diff_density_max         1.212
_refine_diff_density_min         -0.954
_refine_diff_density_rms         0.173
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.09(3)
_refine_ls_extinction_coef       0.0047(8)
_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   1.150
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     261
_refine_ls_number_reflns         6304
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.151
_refine_ls_R_factor_all          0.1267
_refine_ls_R_factor_gt           0.0999
_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^)+37.5575P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2222
_refine_ls_wR_factor_ref         0.2336
_reflns_Friedel_coverage         0.696
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4740
_reflns_number_total             6304
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04158a2.cif
_cod_data_source_block           q
_cod_depositor_comments          'Adding full bibliography for 7134958.cif.'
_cod_original_cell_volume        4115.8(6)
_cod_database_code               7134958
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.91(3)
 0.09(3)
2. 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
3. Restrained distances
 O5-C16A = O5-C16
 1.43 with sigma of 0.02
 C17-C16 = C16A-C17A
 1.52 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C16) = Uanis(C17) = Uanis(C17A) = Uanis(C16A)
5. Others
 Fixed Sof: C16(0.5) H16A(0.5) H16B(0.5) C17(0.5) H17A(0.5) H17B(0.5)
 H17C(0.5) C17A(0.5) H17D(0.5) H17E(0.5) H17F(0.5) C16A(0.5) H16C(0.5) H16D(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C16(H16A,H16B), C16A(H16C,H16D)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C5(H5), C3(H3), C15(H15)
6.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C19(H19A,H19B,
 H19C), C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              56637
_olex2_submission_special_instructions 'No special instructions were received'