Alkylaluminium-catalyzed regioselective hydrophosphinylation of α,β-unsaturated ketones into γ-ketophosphine oxides
Chen, Yiwen; Pang, Ziyuan; Li, Gege; Yang, Xiaobo; Yan, Wenliang; Li, Qifeng; Dong, Xuan; Ma, Xiaoli; Yang, Zhi; Chemical Communications 61 (2025) 9666–9669; doi:10.1039/D5CC01440A

data_7134639
_publ_section_title
;
 Alkylaluminium-catalyzed regioselective hydrophosphinylation of
 \a,\b-unsaturated ketones into \g-ketophosphine oxides
;
_journal_issue                   53
_journal_name_full               'Chemical Communications'
_journal_page_first              9666
_journal_page_last               9669
_journal_paper_doi               10.1039/D5CC01440A
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C36 H55 Al N2'
_chemical_formula_sum            'C36 H55 Al N2'
_chemical_formula_weight         542.80
_chemical_name_systematic        P21/n
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-17
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-02-23 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.621(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4055(4)
_cell_length_b                   25.6624(12)
_cell_length_c                   12.8303(6)
_cell_measurement_reflns_used    8782
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      30.6510
_cell_measurement_theta_min      3.3580
_cell_volume                     3329.7(3)
_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      293(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.783
_diffrn_measurement_device_type  'multiwire proportional'
_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  0.0917
_diffrn_reflns_av_unetI/netI     0.1008
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.783
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            23020
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.783
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.985
_diffrn_reflns_theta_min         3.286
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.083
_exptl_crystal_description       block
_exptl_crystal_F_000             1192
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.845
_refine_diff_density_min         -0.617
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     393
_refine_ls_number_reflns         8301
_refine_ls_number_restraints     41
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.1147
_refine_ls_R_factor_gt           0.0797
_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^)+(0.1108P)^2^+1.0797P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2132
_refine_ls_wR_factor_ref         0.2340
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5623
_reflns_number_total             8301
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01440a2.cif
_cod_data_source_block           11
_cod_depositor_comments
'Adding full bibliography for 7134639--7134642.cif.'
_cod_database_code               7134639
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.971
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C26-C27 \\sim C26-C0
 with sigma of 0.02
 C28-C27 \\sim C28-C0
 with sigma of 0.02
 Al1-C36 \\sim Al1-C38
 with sigma of 0.04
 Al1-C35 \\sim Al1-C37
 with sigma of 0.02
 C35-C36 \\sim C37-C38
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C35 \\sim C37 \\sim C36 \\sim C38: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002 within 2A
4. Rigid body (RIGU) restrains
 C35, C36
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C37, C38
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(H00n)=Sof(H00o)=Sof(H00t)=Sof(H00u)=Sof(C0)=Sof(H0a)=Sof(H0b)=1-FVAR(1)
 Sof(H26a)=Sof(H26b)=Sof(H28a)=Sof(H28b)=Sof(C27)=Sof(H27a)=Sof(H27b)=FVAR(1)
 Sof(C37)=Sof(H1a)=Sof(H1b)=Sof(C38)=Sof(H2a)=Sof(H2b)=Sof(H2c)=1-FVAR(2)
 Sof(C35)=Sof(H35a)=Sof(H35b)=Sof(C36)=Sof(H36a)=Sof(H36b)=Sof(H36c)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C19(H19), C10(H10), C22(H22)
6.b Secondary CH2 refined with riding coordinates:
 C26(H26a,H26b), C26(H00n,H00o), C28(H28a,H28b), C28(H00t,H00u), C29(H29a,
 H29b), C33(H33a,H33b), C35(H35a,H35b), C27(H27a,H27b), C0(H0a,H0b), C37(H1a,
 H1b)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C3(H3), C15(H15), C16(H16), C17(H17)
6.d Idealised Me refined as rotating group:
 C32(H32a,H32b,H32c), C8(H8a,H8b,H8c), C20(H20a,H20b,H20c), C24(H24a,H24b,
 H24c), C9(H9a,H9b,H9c), C11(H11a,H11b,H11c), C21(H21a,H21b,H21c), C12(H12a,
 H12b,H12c), C23(H23a,H23b,H23c), C34(H34a,H34b,H34c), C36(H36a,H36b,H36c),
 C38(H2a,H2b,H2c)
;
_shelx_res_checksum              2082
_shelx_hkl_checksum              8726
_olex2_submission_special_instructions 'No special instructions were received'