Pd(II)-Catalyzed enantioselective C-H olefination toward the synthesis of <i>P</i>-stereogenic phosphinamides.
Chen, Zi-Jia; Fan, Ling-Jie; Xie, Pei-Pei; Qian, Pu-Fan; Hu, Xinquan; Zhou, Tao; Shi, Bing-Feng; Chemical communications (Cambridge, England) 60 (2024) 1623–1626; doi:10.1039/d3cc05052a

data_7132615
_publ_section_title
;
 Pd(II)-Catalyzed enantioselective C-H olefination toward the synthesis of
 <i>P</i>-stereogenic phosphinamides.
;
_journal_issue                   12
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              1623
_journal_page_last               1626
_journal_paper_doi               10.1039/d3cc05052a
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H31 N2 O3 P, H2 O'
_chemical_formula_sum            'C27 H34 N3 O3 P'
_chemical_formula_weight         479.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-07-05 deposited with the CCDC.	2024-01-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.303(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.2201(6)
_cell_length_b                   8.4447(5)
_cell_length_c                   13.8792(9)
_cell_measurement_reflns_used    9918
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      27.11
_cell_measurement_theta_min      2.83
_cell_volume                     1301.28(13)
_computing_cell_refinement       'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service vV6.2.14'
_computing_data_reduction        'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'zju Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0197
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            45938
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.127
_diffrn_reflns_theta_min         2.832
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.138
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.7148
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1285 before and 0.0465 after correction.
The Ratio of minimum to maximum transmission is 0.9588.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_description       block
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.377
_refine_diff_density_min         -0.223
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 2595 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.016(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         5734
_refine_ls_number_restraints     83
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0309
_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^)+(0.0512P)^2^+0.1733P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0798
_refine_ls_wR_factor_ref         0.0803
_reflns_Friedel_coverage         0.870
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                5659
_reflns_number_total             5734
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05052a2.cif
_cod_data_source_block           mo_220315_flj_3_10aa_0m
_cod_depositor_comments          'Adding full bibliography for 7132615.cif.'
_cod_database_code               7132615
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.943
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H24A,H24B,H24C,H24D} of C24, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H27D,H27E,H27F,H4A} of C27A, All O(H) groups
2. Restrained distances
 O4-H4A
 0.87 with sigma of 0.02
 C24-C25 \\sim C24-C25A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 C24-C26 \\sim C24-C26A
 with sigma of 0.04
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
3. Rigid bond restraints
 C24, C25, C26, C27, C25A, C26A, C27A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C24 \\sim C25 \\sim C26 \\sim C27 \\sim C25A \\sim C26A \\sim C27A: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(H24C)=Sof(H24D)=Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26C)=
 Sof(H26D)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(1)
 Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(1)
6.a Free rotating group:
 O4(H4B)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C24(H24A,H24B), C24(H24C,H24D), C25(H25A,H25B), C26(H26A,H26B),
 C25A(H25C,H25D), C26A(H26C,H26D)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22)
6.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C27(H27A,H27B,H27C), C27A(H27D,H27E,H27F)
;
_shelx_res_checksum              5600
_shelx_hkl_checksum              83172
_olex2_submission_special_instructions 'No special instructions were received'