Base-promoted regio- and diastereoselective synthesis of tri- and tetra-substituted homoallenyl phosphine oxides <i>via</i> alkynyl enones.
Zhou, Shaochan; Zou, Haotian; Huang, Xianqiang; Qi, Jialin; Xu, Zhenghu; Organic & biomolecular chemistry 23 (2025) 4718–4724; doi:10.1039/d5ob00446b

data_7160495
_publ_section_title
;
 Base-promoted regio- and diastereoselective synthesis of tri- and
 tetra-substituted homoallenyl phosphine oxides <i>via</i> alkynyl enones.
;
_journal_issue                   19
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4718
_journal_page_last               4724
_journal_paper_doi               10.1039/d5ob00446b
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C41 H30 O2 P'
_chemical_formula_sum            'C41 H30 O2 P'
_chemical_formula_weight         585.62
_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             2025-01-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6403)
;
_audit_update_record
;
2025-01-17 deposited with the CCDC.	2025-04-09 downloaded from the CCDC.
;
_cell_angle_alpha                75.18(4)
_cell_angle_beta                 71.99(3)
_cell_angle_gamma                75.35(4)
_cell_formula_units_Z            2
_cell_length_a                   10.006(12)
_cell_length_b                   12.706(16)
_cell_length_c                   13.425(16)
_cell_measurement_reflns_used    3528
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      22.30
_cell_measurement_theta_min      2.35
_cell_volume                     1541(3)
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            20216
_diffrn_reflns_point_group_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.358
_diffrn_reflns_theta_min         2.354
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.125
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6672
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0806 before and 0.0672 after correction.
The Ratio of minimum to maximum transmission is 0.8953.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       block
_exptl_crystal_F_000             614
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.192
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     416
_refine_ls_number_reflns         5398
_refine_ls_number_restraints     49
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.1452
_refine_ls_R_factor_gt           0.0867
_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^)+(0.0842P)^2^+2.4448P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1955
_refine_ls_wR_factor_ref         0.2341
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3332
_reflns_number_total             5398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00446b2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7160494--7160495.cif.'
_cod_database_code               7160495
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.985
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 P1B-C8 \\sim P1B-C14
 with sigma of 0.01
 P1B-O1 \\sim P1A-O1
 with sigma of 0.01
 C7A-C20 \\sim C7B-C20 \\sim C7B-C6 \\sim C7A-C6
 with sigma of 0.01
 P1B-C7B \\sim P1A-C7A \\sim P1A-C8 \\sim P1B-C8
 with sigma of 0.01
3. Rigid bond restraints
 C7B, C7A, P1B, P1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C7A \\sim C7B \\sim P1B \\sim P1A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
5. Others
 Sof(C7B)=Sof(P1B)=1-FVAR(1)
 Sof(C7A)=Sof(P1A)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C23(H23), C24(H24),
  C25(H25), C26(H26), C27(H27), C31(H31), C32(H32), C33(H33), C34(H34),
 C35(H35), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41)
;
_shelx_res_checksum              87611
_olex2_submission_special_instructions 'No special instructions were received'