Unexpected Insertion of CO2 into the Pentacoordinate P-N Bond: Atherton-Todd-Type Reaction of Hydrospirophosphorane with Amines
Shuxia Cao; Peng Gao; Yanchun Guo; Huamin Zhao; Jun Wang; Yifan Liu; Yufen Zhao; Journal of Organic Chemistry 78 (2013) 11283–11293; doi:10.1021/jo4018342

data_4028753
_publ_section_title
;
 Unexpected Insertion of CO2 into the Pentacoordinate P-N Bond:
 Atherton-Todd-Type Reaction of Hydrospirophosphorane with Amines
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              11283
_journal_page_last               11293
_journal_paper_doi               10.1021/jo4018342
_journal_volume                  78
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H28 N3 O6 P'
_chemical_formula_sum            'C23 H28 N3 O6 P'
_chemical_formula_weight         473.45
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-05-06
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4465)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 101.098(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   11.3068(3)
_cell_length_b                   8.2583(3)
_cell_length_c                   13.1949(4)
_cell_measurement_reflns_used    5049
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.2950
_cell_measurement_theta_min      3.9690
_cell_volume                     1209.03(7)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      291.15
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega   -4.00   25.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000    0.0000 29

  2 omega  -73.00  -48.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000 -180.0000 25

  3 omega  -77.00  -52.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  -30.0000 25

  4 omega  -53.00   29.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   45.0000  150.0000 82

  5 omega  -45.00   28.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000    0.0000 73

  6 omega  -43.00   28.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000   90.0000 71

  7 omega -114.00  -23.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -30.0000 -180.0000 91

  8 omega  -84.00  -36.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -45.0000  -60.0000 48

  9 omega   -5.00   42.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000 -120.0000 47

 10 omega   26.00  101.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000  -90.0000 75

 11 omega   66.00  103.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000  -30.0000 37

 12 omega   47.00   73.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000 -120.0000 26

 13 omega   82.00  108.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -90.0000 26

 14 omega   92.00  118.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -90.0000 26

 15 omega   83.00  110.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -150.0000 27

 16 omega  145.00  174.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -30.0000 29

 17 omega   91.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -60.0000 25

 18 omega  153.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -90.0000 25

 19 omega   82.00  108.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -30.0000 26

 20 omega   88.00  114.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -90.0000 26

 21 omega   61.00   87.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000    0.0000 26

 22 omega   60.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -60.0000 28

 23 omega  112.00  173.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -60.0000 61

 24 omega   83.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -60.0000 26

 25 omega   90.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -30.0000 26

 26 omega   89.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000 -120.0000 27

 27 omega  110.00  151.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  178.0000 -150.0000 41

 28 omega   49.00   90.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -120.0000 41

 29 omega  149.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000   30.0000 29

 30 omega   42.00   96.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000 -180.0000 54

 31 omega  130.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 48

 32 omega   47.00   92.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000 -150.0000 45

 33 omega   84.00  110.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -30.0000 26

 34 omega   89.00  116.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -60.0000 27

 35 omega   87.00  112.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000    0.0000 25

 36 omega  129.00  176.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000    0.0000 47

 37 omega   89.00  117.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -120.0000 28

 38 omega   89.00  115.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -30.0000 26

 39 omega   82.00  108.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 26

 40 omega   91.00  117.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -120.0000 26

 41 omega   92.00  118.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -150.0000 26

 42 omega   89.00  115.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000  -90.0000 26

 43 omega  130.00  174.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -150.0000 44

 44 omega   60.00   89.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -30.0000 29

 45 omega   60.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000   60.0000 28

 46 omega  114.00  177.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000   60.0000 63

 47 omega  108.00  176.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  -83.0000 68
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0848141000
_diffrn_orient_matrix_UB_12      0.0350528000
_diffrn_orient_matrix_UB_13      -0.0758387000
_diffrn_orient_matrix_UB_21      -0.0925103000
_diffrn_orient_matrix_UB_22      -0.0753039000
_diffrn_orient_matrix_UB_23      -0.0885238000
_diffrn_orient_matrix_UB_31      -0.0593177000
_diffrn_orient_matrix_UB_32      0.1670395000
_diffrn_orient_matrix_UB_33      -0.0239247000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0213
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9708
_diffrn_reflns_theta_full        72.33
_diffrn_reflns_theta_max         72.33
_diffrn_reflns_theta_min         3.98
_diffrn_source                   'Enhance (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    1.374
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96121
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_F_000             500
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.189
_refine_diff_density_min         -0.191
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.028(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         4469
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0349
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0574P)^2^+0.0407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.0945
_reflns_number_gt                4240
_reflns_number_total             4469
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo4018342_si_002_6.cif
_cod_data_source_block           20130461
_cod_original_cell_volume        1209.04(6)
_cod_database_code               4028753
_chemical_oxdiff_formula         C20H20N4O4P1
_reflns_odcompleteness_completeness 99.96
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2A), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C12(H12A,H12B), C20(H20A,H20B), C22(H22A,H22B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C)
;