Enantioselective Zn-catalyzed hydrophosphinylation of nitrones: an efficient approach for constructing chiral α-hydroxyamino-phosphine oxides
Luo, Shihui; Yuan, Xinzhu; Cheng, Jiangtao; Yang, Zhiping; Huang, Zhongxing; Wang, Jun (Joelle); Chemical Science 16 (2025) 7051–7056; doi:10.1039/D5SC01453K

data_1574181
_publ_section_title
;
 Enantioselective Zn-catalyzed hydrophosphinylation of nitrones: an
 efficient approach for constructing chiral \a-hydroxyamino-phosphine
 oxides
;
_journal_issue                   16
_journal_name_full               'Chemical Science'
_journal_page_first              7051
_journal_page_last               7056
_journal_paper_doi               10.1039/D5SC01453K
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '1(C26 H23 Br N O2 P), 0.25(C H2 Cl2)'
_chemical_formula_sum            'C26.25 H23.5 Br Cl0.5 N O2 P'
_chemical_formula_weight         513.56
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2024-05-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-06 deposited with the CCDC.	2025-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                79.307(4)
_cell_angle_beta                 73.787(4)
_cell_angle_gamma                73.152(4)
_cell_formula_units_Z            4
_cell_length_a                   10.6028(10)
_cell_length_b                   14.0739(12)
_cell_length_c                   18.2273(16)
_cell_measurement_reflns_used    9686
_cell_measurement_temperature    200.0(2)
_cell_measurement_theta_max      57.00
_cell_measurement_theta_min      2.87
_cell_volume                     2483.4(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_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 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      200.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0725
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            88402
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         57.019
_diffrn_reflns_theta_min         2.210
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_current           3.0
_diffrn_source_power             0.20958
_diffrn_source_type              'Incoatec Metaljet'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.334
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.4982
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1453 before and 0.0925 after correction.
The Ratio of minimum to maximum transmission is 0.6632.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       block
_exptl_crystal_F_000             1050
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.747
_refine_diff_density_min         -0.658
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 7276 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1252
_refine_ls_number_reflns         19869
_refine_ls_number_restraints     530
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0701
_refine_ls_R_factor_gt           0.0628
_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^)+(0.1251P)^2^+0.2404P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1795
_refine_ls_wR_factor_ref         0.1870
_reflns_Friedel_coverage         0.957
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.954
_reflns_number_gt                17262
_reflns_number_total             19869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01453k2.cif
_cod_data_source_block           cxy5656_0m
_cod_depositor_comments          'Adding full bibliography for 1574181.cif.'
_cod_original_formula_sum        'C26.25 H23.50 Br Cl0.50 N O2 P'
_cod_database_code               1574181
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.665
_shelx_estimated_absorpt_t_min   0.616
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 Cl2-C1A
 1.78 with sigma of 0.02
 Cl1-C1B
 1.78 with sigma of 0.02
 Cl4-C1B
 1.77 with sigma of 0.02
 Cl1-C1B = Cl4-C1B
 1.77 with sigma of 0.01
 Cl1-Cl4
 2.92 with sigma of 0.03
 Cl3-C1A
 1.77 with sigma of 0.02
 Cl2-C1A = Cl3-C1A
 1.77 with sigma of 0.01
 Cl7-C1D
 1.78 with sigma of 0.02
 Cl2-Cl3
 2.92 with sigma of 0.03
 Cl8-C1D
 1.77 with sigma of 0.02
 Cl7-C1D = Cl8-C1D
 1.771 with sigma of 0.01
 Cl7-Cl8
 2.916 with sigma of 0.03
 C13-C12 = C17-C12 = C14-C13 = C15-C14 = C16-C15 = C17-C16 = C17A-C12A = C17A-
 C16A = C16A-C15A = C15A-C14A = C14A-C13A = C13A-C12A
 1.39 with sigma of 0.02
 Cl5-C1C
 1.78 with sigma of 0.02
 Cl6-C1C
 1.77 with sigma of 0.02
 Cl5-C1C = Cl6-C1C
 1.77 with sigma of 0.01
 Cl5-Cl6
 2.92 with sigma of 0.03
 Cl1-Cl4
 2.92 with sigma of 0.04
 Cl2-Cl3
 2.92 with sigma of 0.04
 Cl7-Cl8
 2.92 with sigma of 0.04
 Cl5-Cl6
 2.92 with sigma of 0.04
3. Restrained planarity
 C12A, C17A, C16A, C15A, C14A, C13A
 with sigma of 0.1
 C12, C17, C16, C15, C14, C13
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl7 \\sim Cl8 \\sim C1D: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C13 \\sim C12 \\sim C16 \\sim C17 \\sim C14 \\sim C15 \\sim C12A \\sim C17A
\\sim C16A \\sim C15A \\sim C14A \\sim C13A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Cl2 \\sim Cl3 \\sim C1A \\sim Cl1 \\sim Cl4 \\sim C1B \\sim Cl5 \\sim Cl6 \\sim
C1C \\sim Cl7 \\sim Cl8 \\sim C1D: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C1C) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(Cl4)
\\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(Cl8) \\sim Ueq,
Uanis(Cl7) \\sim Ueq, Uanis(C1D) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl2)
\\sim Ueq, Uanis(C1A) \\sim Ueq, : with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C15) = Uanis(C15A)
Uanis(C16) = Uanis(C16A)
Uanis(C17A) = Uanis(C17)
Uanis(C12A) = Uanis(C12)
Uanis(C13A) = Uanis(C13)
Uanis(C14) = Uanis(C14A)
5. Rigid body (RIGU) restrains
 Cl1, Cl4, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2, Cl3, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl7, Cl8, C1D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl5, Cl6, C1C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(Cl2)+Sof(Cl3)+Sof(C1A)+Sof(H1AA)+Sof(H1AB)]+1*[Sof(Cl1)+Sof(Cl4)+
 Sof(C1B)+Sof(H1BA)+Sof(H1BB)]+1*[Sof(Cl5)+Sof(Cl6)+Sof(C1C)+Sof(H1CA)+
 Sof(H1CB)]+1*[Sof(Cl7)+Sof(Cl8)+Sof(C1D)+Sof(H1DA)+Sof(H1DB)]=1 with esd of 0
 Sof(C12A)=Sof(C17A)=Sof(H17A)=Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=
 Sof(C14A)=Sof(H14A)=Sof(C13A)=Sof(H13A)=1-FVAR(1)
 Sof(C13)=Sof(H13)=Sof(C12)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C14)=
 Sof(H14)=Sof(C15)=Sof(H15)=FVAR(1)
 Sof(Cl2)=Sof(Cl3)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=FVAR(2)
 Sof(Cl1)=Sof(Cl4)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=FVAR(3)
 Sof(Cl5)=Sof(Cl6)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=FVAR(4)
 Sof(Cl7)=Sof(Cl8)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=FVAR(5)
7.a Ternary CH refined with riding coordinates:
 C5(H5), C31(H31), C57(H57), C83(H83)
7.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C44(H44A,H44B), C70(H70A,H70B), C96(H96A,H96B), C1A(H1AA,
 H1AB), C1B(H1BA,H1BB), C1C(H1CA,H1CB), C1D(H1DA,H1DB)
7.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C3(H3), C21(H21), C20(H20), C2(H2A), C8(H8), C26(H26), C7(H7),
 C11(H11), C10(H10), C9(H9), C13(H13), C24(H24), C23(H23), C22(H22), C16(H16),
 C17(H17), C14(H14), C15(H15), C29(H29), C28(H28), C33(H33), C34(H34), C51(H51),
  C37(H37), C39(H39), C35(H35), C52(H52), C43(H43), C40(H40), C48(H48),
 C42(H42), C36(H36), C49(H49), C47(H47), C46(H46), C41(H41), C50(H50), C74(H74),
  C75(H75), C55(H55), C65(H65), C77(H77), C72(H72), C73(H73), C76(H76),
 C62(H62), C69(H69), C60(H60), C54(H54), C61(H61), C59(H59), C78(H78), C68(H68),
  C66(H66), C63(H63), C67(H67), C81(H81), C80(H80), C85(H85), C99(H99),
 C98(H98), C103(H103), C100(H100), C88(H88), C87(H87), C104(H104), C91(H91),
 C89(H89), C86(H86), C101(H101), C102(H102), C92(H92), C93(H93), C95(H95),
 C94(H94), C17A(H17A), C16A(H16A), C15A(H15A), C14A(H14A), C13A(H13A)
7.d Idealised tetrahedral OH refined as rotating group:
 O2(H2), O4(H4), O6(H6), O8(H8A)
;
_shelx_res_checksum              39503
_olex2_submission_special_instructions 'No special instructions were received'