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_7133222
_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         'C29.002 H25.669 N O4.001 P, C29 H26 N O4 P'
_chemical_formula_sum            'C58 H51.67 N2 O8 P2'
_chemical_formula_weight         966.67
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-12-07
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-12 deposited with the CCDC.	2024-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.3419(5)
_cell_length_b                   21.1766(5)
_cell_length_c                   21.9827(5)
_cell_measurement_reflns_used    9928
_cell_measurement_temperature    200.00
_cell_measurement_theta_max      68.06
_cell_measurement_theta_min      4.18
_cell_volume                     9935.1(4)
_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      200.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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  0.0695
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            129557
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.366
_diffrn_reflns_theta_min         3.562
_diffrn_source_current           1.2
_diffrn_source_power             0.06
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.271
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.7032
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0879 before and 0.0657 after correction.
The Ratio of minimum to maximum transmission is 0.9337.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       needle
_exptl_crystal_F_000             4062
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.309
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.176
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     841
_refine_ls_number_reflns         9094
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.176
_refine_ls_R_factor_all          0.0719
_refine_ls_R_factor_gt           0.0652
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0382P)^2^+12.3594P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1534
_refine_ls_wR_factor_ref         0.1565
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7954
_reflns_number_total             9094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02638a2.cif
_cod_data_source_block           11
_cod_depositor_comments
'Adding full bibliography for 7133221--7133223.cif.'
_cod_database_code               7133222
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C26(0.5) C0(0.5) H0(0.5) C22(0.5) H22(0.5) C23(0.5) H23(0.5)
 C24(0.5) H24(0.5) C25(0.5) H25(0.5) C27(0.5) C30(0.5) H30(0.5) C32(0.5)
 H32(0.5) C31(0.5) H31(0.5) C29(0.5) H29(0.5) C28(0.5) H28(0.5) C2(0.667)
 H2(0.667) O00Y(0.667) C9(0.667) H9(0.667) H01E(0.667) C12(0.667) O01G(0.5)
 C8(0.667) O3(0.667) C11(0.667) H11(0.667) O01T(0.333333) O01U(0.5) O01W(0.5)
 O01X(0.5) C7(0.667) H7A(0.667) H7B(0.667) H7C(0.667) C020(0.5) H02D(0.5)
 H02E(0.5) H02F(0.5) O021(0.333333) C022(0.5) H02G(0.5) H02H(0.5) H02I(0.5)
 C023(0.333333) H02A(0.333333) H02B(0.333333) H02C(0.333333) C4(0.333333)
 H4(0.333333) C5(0.333333) H5(0.333333) C6(0.333333) C10(0.333333)
 H10(0.333333) C18(0.333333) C14(0.5) H14(0.5) C1(0.5) H1(0.5) C13(0.5) C3(0.5)
 C15(0.5) C17(0.5) H17(0.5) C20(0.5) H20(0.5) C16(0.5) H16(0.5) C19(0.5)
 C21(0.5) H21(0.5) C1A(0.5) H1A(0.5) C1F(0.5) C1E(0.5) H1E(0.5) C1D(0.5)
 H1D(0.5) C1C(0.5) H1C(0.5) C1B(0.5) H1B(0.5) C1G(0.5) C1H(0.5) H1H(0.5)
 C1I(0.5) H1I(0.5) C1K(0.5) H1K(0.5) C1L(0.5) H1L(0.5) C1J(0.5) H1J(0.5)
3.a Ternary CH refined with riding coordinates:
 C009(H009), C00C(H00D), C00D(H00E), C00F(H00F)
3.b Aromatic/amide H refined with riding coordinates:
 C0(H0), C22(H22), C23(H23), C24(H24), C25(H25), C00L(H00L), C30(H30),
 C32(H32), C31(H31), C29(H29), C28(H28), C00O(H00O), C00P(H00P), C00S(H00S),
 C2(H2), C00U(H00U), C00V(H00V), C00X(H00X), C00Z(H00Z), C011(H011), C012(H012),
  C013(H013), C014(H014), C015(H015), C9(H9), C017(H017), C019(H019),
 C01D(H01D), C01E(H01E), C01I(H01I), C01J(H01J), C11(H11), C01Q(H01Q), C4(H4),
 C5(H5), C10(H10), C14(H14), C1(H1), C17(H17), C20(H20), C16(H16), C21(H21),
 C1A(H1A), C1E(H1E), C1D(H1D), C1C(H1C), C1B(H1B), C1H(H1H), C1I(H1I), C1K(H1K),
  C1L(H1L), C1J(H1J)
3.c Fitted hexagon refined as free rotating group:
 C26(C0,C22,C23,C24,C25), C27(C30,C32,C31,C29,C28), C1A(C1F,C1E,C1D,C1C,C1B),
 C1G(C1H,C1I,C1K,C1L,C1J)
3.d Idealised Me refined as rotating group:
 C00Q(H00A,H00B,H00C), C00R(H00G,H00H,H00I), C7(H7A,H7B,H7C), C020(H02D,H02E,
 H02F), C022(H02G,H02H,H02I), C023(H02A,H02B,H02C)
;
_shelx_res_checksum              65617
_shelx_hkl_checksum              11015
_olex2_submission_special_instructions 'No special instructions were received'