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_7134641
_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_absolute_configuration ad
_chemical_formula_moiety         'C28 H39 Al N2'
_chemical_formula_sum            'C28 H39 Al N2'
_chemical_formula_weight         430.59
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-24
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-02-24 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   16.5787(4)
_cell_length_b                   20.7155(4)
_cell_length_c                   29.8150(6)
_cell_measurement_reflns_used    21016
_cell_measurement_temperature    99.9(2)
_cell_measurement_theta_max      30.6750
_cell_measurement_theta_min      2.0900
_cell_volume                     10239.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_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_environment      N~2~
_diffrn_ambient_temperature      99.9(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.815
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -17.00  11.00   0.50   13.00    --    3.17 -69.00 -64.00   56
  2  \w    -18.00  36.00   0.50   13.00    --    3.17 -99.00  60.00  108
  3  \w     -8.00  18.00   0.50   13.00    --    3.17 -99.00  90.00   52
  4  \w    -18.00  36.00   0.50   13.00    --    3.17 -99.00-180.00  108
  5  \w    -32.00  -7.00   0.50   13.00    --   -7.00 -38.00  90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0053291000
_diffrn_orient_matrix_UB_12      0.0266999000
_diffrn_orient_matrix_UB_13      0.0146076000
_diffrn_orient_matrix_UB_21      -0.0415681000
_diffrn_orient_matrix_UB_22      0.0009873000
_diffrn_orient_matrix_UB_23      -0.0055569000
_diffrn_orient_matrix_UB_31      -0.0085539000
_diffrn_orient_matrix_UB_32      -0.0214117000
_diffrn_orient_matrix_UB_33      0.0179429000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.815
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            66871
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.772
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.838
_diffrn_reflns_theta_min         1.966
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63879
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.140a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.117
_exptl_crystal_description       block
_exptl_crystal_F_000             3744
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.481
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 7253 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1153
_refine_ls_number_reflns         24858
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0692
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0668P)^2^+0.8879P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1108
_refine_ls_wR_factor_ref         0.1184
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.723
_reflns_number_gt                19612
_reflns_number_total             24858
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01440a2.cif
_cod_data_source_block           exp_2769_auto
_cod_depositor_comments
'Adding full bibliography for 7134639--7134642.cif.'
_cod_database_code               7134641
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N Al'
_chemical_oxdiff_usercomment     'C H N Al'
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.986
_olex2_refinement_description
;
1.a Secondary CH2 refined with riding coordinates:
 C95(H95A,H95B), C16(H16A,H16B), C96(H96A,H96B), C42(H42A,H42B), C39(H39A,
 H39B), C13(H13A,H13B), C97(H97A,H97B), C98(H98A,H98B), C72(H72A,H72B),
 C41(H41A,H41B), C71(H71A,H71B), C40(H40A,H40B), C69(H69A,H69B), C14(H14A,H14B),
  C70(H70A,H70B), C15(H15A,H15B)
1.b Aromatic/amide H refined with riding coordinates:
 C106(H106), C63(H63), C31(H31), C77(H77), C79(H79), C91(H91), C24(H24),
 C21(H21), C7(H7), C104(H104), C3(H3), C49(H49), C35(H35), C52(H52), C59(H59),
 C87(H87)
1.c Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C76(H76A,H76B,H76C), C27(H27A,H27B,H27C), C26(H26A,H26B,
 H26C), C92(H92A,H92B,H92C), C45(H45A,H45B,H45C), C36(H36A,H36B,H36C), C28(H28A,
 H28B,H28C), C81(H81A,H81B,H81C), C83(H83A,H83B,H83C), C67(H67A,H67B,H67C),
 C54(H54A,H54B,H54C), C20(H20A,H20B,H20C), C57(H57A,H57B,H57C), C64(H64A,H64B,
 H64C), C10(H10A,H10B,H10C), C37(H37A,H37B,H37C), C55(H55A,H55B,H55C), C8(H8A,
 H8B,H8C), C101(H10D,H10E,H10F), C84(H84A,H84B,H84C), C93(H93A,H93B,H93C),
 C65(H65A,H65B,H65C), C111(H11A,H11B,H11C), C23(H23A,H23B,H23C), C48(H48A,H48B,
 H48C), C108(H10G,H10H,H10I), C9(H9A,H9B,H9C), C109(H10J,H10K,H10L), C110(H11D,
 H11E,H11F), C29(H29A,H29B,H29C), C82(H82A,H82B,H82C), C85(H85A,H85B,H85C),
 C1(H1A,H1B,H1C), C112(H11G,H11H,H11I), C51(H51A,H51B,H51C)
;
_shelx_res_checksum              49493
_shelx_hkl_checksum              87841
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.407
_oxdiff_exptl_absorpt_empirical_full_min 0.727