Manganese(III)-promoted highly stereoselective phosphorylation of acyclic tertiary enamides to synthesize <i>E</i>-selective β-phosphoryl enamides.
Xu, Xin-Ming; Li, Wenzhong; Li, Qiwei; Chen, Sen; Zhang, Xuesi; Yang, Bin; Wang, Wei-Li; Organic & biomolecular chemistry 20 (2022) 5566–5574; doi:10.1039/d2ob00980c

data_7158759
_publ_section_title
;
 Manganese(III)-promoted highly stereoselective phosphorylation of acyclic
 tertiary enamides to synthesize <i>E</i>-selective \b-phosphoryl
 enamides.
;
_journal_issue                   28
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5566
_journal_page_last               5574
_journal_paper_doi               10.1039/d2ob00980c
_journal_volume                  20
_journal_year                    2022
_chemical_formula_moiety         'C34 H28 N O2 P, C3 H7'
_chemical_formula_sum            'C37 H35 N O2 P'
_chemical_formula_weight         556.63
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-08-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-04-30 deposited with the CCDC.	2022-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                79.0240(10)
_cell_angle_beta                 75.1120(10)
_cell_angle_gamma                74.3280(10)
_cell_formula_units_Z            2
_cell_length_a                   9.27560(10)
_cell_length_b                   10.20610(10)
_cell_length_c                   17.1546(2)
_cell_measurement_reflns_used    16425
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      75.1170
_cell_measurement_theta_min      4.9460
_cell_volume                     1498.29(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      170.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.955
_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    -89.00 -12.00   0.50    0.05    --  -47.57 123.00  51.00  154
  2  \w   -104.00 -69.00   0.50    0.05    --  -47.57 149.00-145.00   70
  3  \w   -118.00 -57.00   0.50    0.05    --  -47.57-149.00 168.00  122
  4  \w     32.00  57.00   0.50    0.05    --   47.57-123.00 -28.00   50
  5  \w     69.00  95.00   0.50    0.05    --   47.57 149.00-145.00   52
  6  \w   -146.00-121.00   0.50    0.05    --  -99.00-123.00 -28.00   50
  7  \w    -64.00 -27.00   0.50    0.05    --  -99.00 149.00-145.00   74
  8  \w   -128.00 -69.00   0.50    0.05    --  -99.00 149.00-145.00  118
  9  \w   -103.00 -71.00   0.50    0.05    --  -99.00 123.00  51.00   64
 10  \w    -68.00 -26.00   0.50    0.05    --  -99.00 123.00  51.00   84
 11  \w     81.00 129.00   0.50    0.05    --  103.25-149.00 168.00   96
 12  \w     93.00 126.00   0.50    0.05    --  103.25 123.00  51.00   66
 13  \w     31.00 110.00   0.50    0.05    --  103.25-123.00 -28.00  158
 14  \w    112.00 138.00   0.50    0.05    --  103.25 149.00-145.00   52
 15  \w   -114.00 -74.00   0.50    0.05    --  -47.57-125.00  60.00   80
 16  \w    -22.00  25.00   0.50    0.05    --  -47.57  19.00-120.00   94
 17  \w   -119.00 -50.00   0.50    0.05    --  -47.57 -77.00 -90.00  138
 18  \w     47.00  72.00   0.50    0.05    --   47.57-149.00 168.00   50
 19  \w     46.00 103.00   0.50    0.05    --   47.57  57.00 -90.00  114
 20  \w   -158.00 -74.00   0.50    0.05    --  -99.00-125.00 -60.00  168
 21  \w   -168.00 -86.00   0.50    0.05    --  -99.00 -30.00  30.00  164
 22  \w   -167.00 -85.00   0.50    0.05    --  -99.00 -61.00   0.00  164
 23  \w   -111.00 -84.00   0.50    0.05    --  -99.00 125.00 150.00   54
 24  \w    -56.00 -26.00   0.50    0.05    --  -99.00  61.00 -90.00   60
 25  \w    -68.00 -29.00   0.50    0.05    --  -99.00  61.00 150.00   78
 26  \w   -160.00-121.00   0.50    0.05    --  -99.00-125.00 -90.00   78
 27  \w   -110.00 -84.00   0.50    0.05    --  -99.00-125.00 -90.00   52
 28  \w   -136.00-110.00   0.50    0.05    --  -99.00-149.00 168.00   52
 29  \w    -64.00 -38.00   0.50    0.05    --  -99.00 125.00 150.00   52
 30  \w   -168.00 -85.00   0.50    0.05    --  -99.00 -15.00 120.00  166
 31  \w     42.00  68.00   0.50    0.05    --  103.25 -77.00 -60.00   52
 32  \w    141.00 167.00   0.50    0.05    --  103.25 125.00 150.00   52
 33  \w     82.00 108.00   0.50    0.05    --  103.25 125.00 150.00   52
 34  \w    136.00 169.00   0.50    0.05    --  103.25 125.00   0.00   66
 35  \w     84.00 128.00   0.50    0.05    --  103.25 125.00   0.00   88
 36  \w     33.00 110.00   0.50    0.05    --  103.25-125.00   0.00  154
 37  \w    114.00 152.00   0.50    0.05    --  103.25  15.00   0.00   76
 38  \w     32.00  75.00   0.50    0.05    --  103.25 -61.00-180.00   86
 39  \w     80.00 106.00   0.50    0.05    --  103.25 -77.00 150.00   52
 40  \w     68.00 100.00   0.50    0.05    --  103.25 -94.00 150.00   64
 41  \w     33.00  73.00   0.50    0.05    --  103.25 -77.00 150.00   80
 42  \w     80.00 106.00   0.50    0.05    --  103.25 -77.00 -60.00   52
 43  \w     51.00 111.00   0.50    0.05    --  103.25-125.00-180.00  120
 44  \w     37.00  62.00   0.50    0.05    --  103.25 -61.00-150.00   50
 45  \w     31.00  68.00   0.50    0.05    --  103.25 -61.00 -60.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0225082000
_diffrn_orient_matrix_UB_12      0.0542590000
_diffrn_orient_matrix_UB_13      -0.0914218000
_diffrn_orient_matrix_UB_21      0.0017882000
_diffrn_orient_matrix_UB_22      -0.1422482000
_diffrn_orient_matrix_UB_23      -0.0187416000
_diffrn_orient_matrix_UB_31      -0.1752799000
_diffrn_orient_matrix_UB_32      0.0426870000
_diffrn_orient_matrix_UB_33      0.0086132000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0211
_diffrn_reflns_av_unetI/netI     0.0159
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            19773
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.079
_diffrn_reflns_theta_min         4.967
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.069
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47451
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.234
_exptl_crystal_description       plate
_exptl_crystal_F_000             590
_exptl_crystal_size_max          0.77
_exptl_crystal_size_mid          0.45
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.214
_refine_diff_density_min         -0.669
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         5906
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0545
_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^)+(0.0867P)^2^+1.2366P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1527
_refine_ls_wR_factor_ref         0.1537
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5736
_reflns_number_total             5906
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob00980c2.cif
_cod_data_source_block           tx7033
_cod_depositor_comments          'Adding full bibliography for 7158759.cif.'
_cod_database_code               7158759
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONClP
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.493
_reflns_odcompleteness_completeness 99.42
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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) groups
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C40(H40A,H40B), C41(H41A,H41B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C26(H26), C34(H34), C6(H6), C22(H22), C25(H25), C5(H5), C20(H20),
 C2(H2), C38(H38), C35(H35), C32(H32), C19(H19), C4(H4), C3(H3), C24(H24),
 C23(H23), C16(H16), C36(H36), C28(H28), C18(H18), C31(H31), C37(H37), C17(H17),
  C30(H30), C29(H29)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              71980
_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 1.917
_oxdiff_exptl_absorpt_empirical_full_min 0.510