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_7134640
_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         'C30 H43 Al N2'
_chemical_formula_sum            'C30 H43 Al N2'
_chemical_formula_weight         458.64
_space_group_crystal_system      orthorhombic
_space_group_IT_number           39
_space_group_name_Hall           'A 2 -2b'
_space_group_name_H-M_alt        'A e m 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-15
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6163(7)
_cell_length_b                   22.5091(9)
_cell_length_c                   7.7370(5)
_cell_measurement_reflns_used    5742
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      30.4190
_cell_measurement_theta_min      3.8080
_cell_volume                     2719.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.140a 64-bit (release 03-10-2024))'
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.828
_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     -9.00  44.00   0.50    3.77    --    3.05  38.00-120.00  106
  2  \w    -70.00 -17.00   0.50    3.77    --   -7.11 -57.00-150.00  106
  3  \w     -3.00  31.00   0.50    3.77    --    3.05 -99.00   0.00   68
  4  \w    -78.00 -11.00   0.50    3.77    --   -7.11 -19.00  60.00  134
;
_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      0.0445044000
_diffrn_orient_matrix_UB_12      -0.0010386500
_diffrn_orient_matrix_UB_13      -0.0181157500
_diffrn_orient_matrix_UB_21      0.0063552000
_diffrn_orient_matrix_UB_22      0.0257717000
_diffrn_orient_matrix_UB_23      0.0508998000
_diffrn_orient_matrix_UB_31      0.0065010000
_diffrn_orient_matrix_UB_32      -0.0181473000
_diffrn_orient_matrix_UB_33      0.0739767000
_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  0.0436
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.828
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            8882
_diffrn_reflns_point_group_measured_fraction_full 0.961
_diffrn_reflns_point_group_measured_fraction_max 0.732
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.081
_diffrn_reflns_theta_min         3.621
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.094
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64069
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.120
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.364
_refine_diff_density_min         -0.242
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 1104 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.7(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         3279
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0636
_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^)+(0.0642P)^2^+5.4975P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1627
_refine_ls_wR_factor_ref         0.1645
_reflns_Friedel_coverage         0.654
_reflns_Friedel_fraction_full    0.920
_reflns_Friedel_fraction_max     0.622
_reflns_number_gt                3073
_reflns_number_total             3279
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01440a2.cif
_cod_data_source_block           exp_1592
_cod_depositor_comments
'Adding full bibliography for 7134639--7134642.cif.'
_cod_original_sg_symbol_Hall     'A 2 -2c'
_cod_original_sg_symbol_H-M      'A b m 2'
_cod_database_code               7134640
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_usercomment     'C H Al N '
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.988
_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. Shared sites
{C8, C8A}
3. Restrained distances
 C16-C15 \\sim C16A-C15
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C15 \\sim C16 \\sim C16A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C8) = Uanis(C8A)
5. Others
 Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
 Fixed Sof: H2A(0.5) H2B(0.5) H2C(0.5) C8(0.5) H8A(0.5) H8B(0.5) H5A(0.5)
 H5B(0.5) H1A(0.5) H1B(0.5) H1C(0.5) C6(0.5) H6A(0.5) H6B(0.5) C7(0.5) H7A(0.5)
 H7B(0.5) C8A(0.5) H8AA(0.5) H8AB(0.5) H8AC(0.5)
6.a Riding coordinates:
 C5(H5A,H5B)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C17(H17A,H17B), C15(H15A,H15B), C15(H15C,H15D), C6(H6A,H6B),
 C7(H7A,H7B)
6.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C12(H12), C11(H11)
6.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C1(H1A,H1B,H1C), C18(H18A,H18B,H18C), C16(H16A,H16B,H16C),
 C16A(H16D,H16E,H16F), C8A(H8AA,H8AB,H8AC)
;
_shelx_res_checksum              33558
_shelx_hkl_checksum              35802
_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 1.653
_oxdiff_exptl_absorpt_empirical_full_min 0.510