Electrochemical synthesis of phosphorylated azaspiro[4.5]di/trienones through dearomative spirocyclization.
Zhou, Xiaocong; Wang, Jian; Ma, Dumei; Shen, Yirui; Zhao, Yufen; Wu, Ju; Chemical communications (Cambridge, England) 60 (2024) 7351–7354; doi:10.1039/d4cc02638a

data_7133221
_publ_section_title
;
 Electrochemical synthesis of phosphorylated azaspiro[4.5]di/trienones
 through dearomative spirocyclization.
;
_journal_issue                   57
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7351
_journal_page_last               7354
_journal_paper_doi               10.1039/d4cc02638a
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C39 H35 N2 O4 P, C H Cl3'
_chemical_formula_sum            'C41 H35 Cl3 N0.5 O5 P'
_chemical_formula_weight         752.01
_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
_audit_creation_date             2024-03-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-03-26 deposited with the CCDC.	2024-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                101.7810(10)
_cell_angle_beta                 98.9850(10)
_cell_angle_gamma                114.4810(10)
_cell_formula_units_Z            2
_cell_length_a                   11.7184(2)
_cell_length_b                   12.5450(2)
_cell_length_c                   14.6960(2)
_cell_measurement_reflns_used    9904
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      66.55
_cell_measurement_theta_min      3.19
_cell_volume                     1853.15(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      200.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_av_unetI/netI     0.0330
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            41477
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.730
_diffrn_reflns_theta_max         66.730
_diffrn_reflns_theta_min         3.190
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.013
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6736
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1080 before and 0.0616 after correction.
The Ratio of minimum to maximum transmission is 0.8948.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.348
_exptl_crystal_description       block
_exptl_crystal_F_000             781
_exptl_crystal_size_max          0.079
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.293
_refine_diff_density_min         -0.272
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         6548
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0481P)^2^+0.6690P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5542
_reflns_number_total             6548
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02638a2.cif
_cod_data_source_block           111
_cod_depositor_comments
'Adding full bibliography for 7133221--7133223.cif.'
_cod_original_cell_volume        1853.15(5)
_cod_original_formula_sum        'C41 H35 Cl3 N0.50 O5 P'
_cod_database_code               7133221
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.826
_shelx_estimated_absorpt_t_min   0.797
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 N009, C00M
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 N009, C00R
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 N008, C00C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C01C, C018
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(N009) \\sim Ueq, Uanis(C00M) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C00C) \\sim Ueq, Uanis(N008) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
4.a Ternary CH refined with riding coordinates:
 C00K(H00K), C015(H015)
4.b Aromatic/amide H refined with riding coordinates:
 N009(H009), C00I(H00I), C00J(H00J), C00L(H00L), C00O(H00O), C00P(H00P),
 C00Q(H00Q), C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X),
 C00Y(H00Y), C00Z(H00Z), C010(H010), C014(H014), C016(H016), C017(H017),
 C018(H018), C019(H019), C01A(H01J), C01B(H01K), C01C(H01L), C01D(H01M),
 C01E(H01N)
4.c Idealised Me refined as rotating group:
 C011(H01A,H01B,H01C), C012(H01D,H01E,H01F), C013(H01G,H01H,H01I)
;
_shelx_res_checksum              55163
_shelx_hkl_checksum              23121
_olex2_submission_special_instructions 'No special instructions were received'