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_4028752
_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     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-05-29
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 98.553(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   16.1499(3)
_cell_length_b                   6.10696(15)
_cell_length_c                   25.0130(7)
_cell_measurement_reflns_used    5694
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      67.4660
_cell_measurement_theta_min      3.4890
_cell_volume                     2439.52(10)
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -25.00   38.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.4048   37.0000  -60.0000 126

  2 omega  -49.00   39.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.4048   37.0000   60.0000 176

  3 omega   67.00  108.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       33.4048  178.0000 -120.0000 82

  4 omega   14.00   39.00   0.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       33.4048   57.0000   90.0000 50

  5 omega  -72.00  -37.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   77.0000  -90.0000 70

  6 omega  -57.00  -26.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -61.0000 -150.0000 62

  7 omega -102.00  -19.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -76.0000  148.9058 166

  8 omega  -44.00  -19.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -45.0000 -180.0000 50

  9 omega -118.00  -91.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000 -120.0000 54

 10 omega  -84.00  -58.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -61.0000 -180.0000 52

 11 omega  -80.00  -36.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000 -120.0000 88

 12 omega  -55.00  -27.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -61.0000 -180.0000 56

 13 omega   72.00  105.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000 -150.0000 66

 14 omega   77.00  169.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000   60.0000 184

 15 omega  119.00  172.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000   90.0000 106

 16 omega   81.00  107.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   61.0000  120.0000 52

 17 omega  120.00  165.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000  150.0000 90

 18 omega   72.00   98.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000   90.0000 52

 19 omega   39.00   75.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609  -45.0000   90.0000 72

 20 omega   80.00  106.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   61.0000 -150.0000 52

 21 omega   72.00   98.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000  150.0000 52

 22 omega   80.00  106.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   61.0000   90.0000 52

 23 omega   80.00  105.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   61.0000  150.0000 50

 24 omega   81.00  108.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   61.0000 -180.0000 54

 25 omega   54.00   97.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609  -45.0000  120.0000 86

 26 omega   82.00  132.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609  -77.0000  -90.0000 100

 27 omega  105.00  171.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000 -180.0000 132

 28 omega   85.00  110.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   45.0000   90.0000 50

 29 omega  120.00  171.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000  120.0000 102

 30 omega   32.00   98.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609  -45.0000   30.0000 132

 31 omega   79.00  104.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   45.0000  150.0000 50

 32 omega   79.00  105.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   30.0000  150.0000 52

 33 omega   72.00   98.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000  120.0000 52

 34 omega   77.00  110.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   30.0000 -150.0000 66

 35 omega   79.00  104.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   45.0000  120.0000 50

 36 omega   79.00  105.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   45.0000 -180.0000 52

 37 omega  117.00  158.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000 -150.0000 82

 38 omega   56.00  108.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609  -94.0000   90.0000 104

 39 omega   76.00  105.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   30.0000 -180.0000 58

 40 omega   81.00  107.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   30.0000 -120.0000 52

 41 omega   72.00   98.00   0.5000   11.0000
omega____ theta____ kappa____ phi______ frames
    -      102.1609   77.0000 -180.0000 52
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0423780000
_diffrn_orient_matrix_UB_12      0.0847355000
_diffrn_orient_matrix_UB_13      -0.0472614000
_diffrn_orient_matrix_UB_21      0.0864796000
_diffrn_orient_matrix_UB_22      -0.0258866000
_diffrn_orient_matrix_UB_23      0.0348484000
_diffrn_orient_matrix_UB_31      0.0057484000
_diffrn_orient_matrix_UB_32      -0.2361776000
_diffrn_orient_matrix_UB_33      -0.0207409000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0331
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            16671
_diffrn_reflns_theta_full        63.68
_diffrn_reflns_theta_max         63.68
_diffrn_reflns_theta_min         3.06
_diffrn_source                   'Enhance (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    1.362
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87744
_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    1.289
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     620
_refine_ls_number_reflns         7585
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0503
_refine_ls_R_factor_gt           0.0429
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0627P)^2^+0.0453P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1070
_refine_ls_wR_factor_ref         0.1120
_reflns_number_gt                6609
_reflns_number_total             7585
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo4018342_si_002_5.cif
_cod_data_source_block           20130584
_cod_database_code               4028752
_chemical_oxdiff_formula         C20H20N4O4P2
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     63.60
_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. Uiso/Uaniso restraints and constraints
Uanis(C21') = Uanis(C1A)
3. others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(H20C)=Sof(H20D)=1-FVAR(1)
 Sof(H20A)=Sof(H20B)=Sof(C21')=Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C2(H2A), C2'(H2'A), C11(H11), C11'(H11')
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C3'(H3'A,H3'B), C12(H12C,H12D), C12'(H12A,H12B), C20(H20E,H20F),
 C20'(H20C,H20D), C20'(H20A,H20B), C22(H22C,H22D), C22'(H22A,H22B)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C5'(H5'), C6(H6), C6'(H6'), C7(H7), C7'(H7'), C8(H8), C8'(H8'),
 C9(H9), C9'(H9'), C14(H14), C14'(H14'), C15(H15), C15'(H15'), C16(H16),
 C16'(H16'), C17(H17), C17'(H17'), C18(H18), C18'(H18')
4.d Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), C21(H21D,H21E,H21F), C21'(H21A,H21B,H21C), C23(H23D,H23E,
 H23F), C23'(H23A,H23B,H23C)
;