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_4028750
_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         'C19 H36 N3 O6 P'
_chemical_formula_sum            'C19 H36 N3 O6 P'
_chemical_formula_weight         433.48
_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             2012-12-04
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:22:26, GUI svn.r4372)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 97.9548(18)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   10.02685(16)
_cell_length_b                   10.35683(16)
_cell_length_c                   23.9983(5)
_cell_measurement_reflns_used    6567
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      66.9618
_cell_measurement_theta_min      3.7164
_cell_volume                     2468.16(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_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 0.9996
_diffrn_measured_fraction_theta_max 0.9979
_diffrn_measurement_details
;
  1 omega  -38.00  -12.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   19.0000 -180.0000 52

  2 omega    1.00   36.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000 -180.0000 70

  3 omega   44.00   70.00   0.5000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   19.0000 -180.0000 52

  4 omega  -31.00   27.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000 -120.0000 116

  5 omega  -28.00   18.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000  -60.0000 92

  6 omega  -91.00  -21.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -61.0000  150.0000 140

  7 omega  -30.00   20.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000   90.0000 100

  8 omega  -35.00    8.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000    0.0000 86

  9 omega -106.00  -35.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000  -90.0000 142

 10 omega -110.00  -36.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  178.0000   60.0000 148

 11 omega   32.00   90.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   42.0000 -124.0000 116

 12 omega   37.00  118.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000  -90.0000 162

 13 omega   83.00  116.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000 -150.0000 66

 14 omega   89.00  114.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   42.0000 -124.0000 50

 15 omega   41.00   98.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  -30.0000 114

 16 omega  125.00  173.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -120.0000 96

 17 omega   82.00  108.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 52

 18 omega   90.00  178.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -180.0000 176

 19 omega   89.00  116.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   43.0000 -149.9062 54

 20 omega   90.00  116.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -180.0000 52

 21 omega  138.00  171.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  -30.0000 66

 22 omega   41.00  103.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000    0.0000 124

 23 omega   83.00  120.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -90.0000 74

 24 omega   89.00  119.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   45.0000 -120.0000 60

 25 omega  102.00  178.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000    0.0000 152

 26 omega   83.00  111.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000 -120.0000 56

 27 omega   82.00  108.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -180.0000 52

 28 omega   83.00  123.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000 -180.0000 80

 29 omega   91.00  162.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  150.0000 142

 30 omega   90.00  116.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -120.0000 52

 31 omega   82.00  107.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -150.0000 50

 32 omega   56.00   83.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -30.0000 -150.0000 54

 33 omega  140.00  166.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -150.0000 52

 34 omega   90.00  116.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  120.0000 52

 35 omega   90.00  115.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -150.0000 50

 36 omega   82.00  108.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  120.0000 52

 37 omega  117.00  160.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  120.0000 86

 38 omega   85.00  111.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  150.0000 52

 39 omega   41.00   95.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000   30.0000 108

 40 omega   40.00  116.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  -60.0000 152

 41 omega  153.00  178.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   46.0000 -110.1334 50

 42 omega   59.00  168.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   15.0000  -30.0000 218

 43 omega   89.00  115.00   0.5000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   46.0000 -110.1334 52
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1351542000
_diffrn_orient_matrix_UB_12      -0.0719435000
_diffrn_orient_matrix_UB_13      -0.0023817000
_diffrn_orient_matrix_UB_21      0.0312986000
_diffrn_orient_matrix_UB_22      -0.0289545000
_diffrn_orient_matrix_UB_23      0.0634384000
_diffrn_orient_matrix_UB_31      -0.0694413000
_diffrn_orient_matrix_UB_32      0.1269286000
_diffrn_orient_matrix_UB_33      0.0131116000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            20047
_diffrn_reflns_theta_full        67.07
_diffrn_reflns_theta_max         67.07
_diffrn_reflns_theta_min         3.72
_diffrn_source                   'Enhance (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    1.289
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91949
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.167
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.544
_refine_diff_density_min         -0.246
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_coef       0.00064(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     547
_refine_ls_number_reflns         8522
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0529
_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^)+(0.0972P)^2^+0.2366P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1452
_refine_ls_wR_factor_ref         0.1520
_reflns_number_gt                7610
_reflns_number_total             8522
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo4018342_si_002_3.cif
_cod_data_source_block           201211217a
_cod_database_code               4028750
_chemical_oxdiff_formula         C30H30O4N4P1
_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:
  H2'A of C2', H2A of C2, {H13C,H13D} of C13, {H12A,H12B} of C12', H2' of N2',
   H2 of N2, H1' of N1', H1 of N1, {H13A,H13B} of C13', H3' of C3', H3 of C3,
  {H18E,H18F} of C18, {H18C,H18D,H18A,H18B} of C18', {H12C,H12D} of C12, {H17A,
  H17B} of C17', {H17C,H17D} of C17, H8 of C8, H7 of C7, {H14C,H14D} of C14,
  {H16C,H16D} of C16, {H16A,H16B} of C16', {H14A,H14B} of C14', H8' of C8', H7'
  of C7'
 At 1.5 times of:
  {H4A,H4B,H4C} of C4, {H19A,H19B,H19C} of C19A, {H5A,H5B,H5C} of C5, {H10A,
  H10B,H10C} of C10', {H9'A,H9'B,H9'C} of C9', {H15D,H15E,H15F} of C15, {H10D,
  H10E,H10F} of C10, {H19G,H19H,H19I} of C19, {H19D,H19E,H19F} of C19', {H5'A,
  H5'B,H5'C} of C5', {H15A,H15B,H15C} of C15', {H4'A,H4'B,H4'C} of C4', {H9A,
  H9B,H9C} of C9
2. Restrained distances
 C14'-C13'
 1.5 with sigma of 0.02
 C18'-C19A
 1.55 with sigma of 0.02
 C18'-C19'
 1.55 with sigma of 0.02
 C14-C15
 1.52 with sigma of 0.02
 C14-C13
 1.52 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C19') ~ Ueq, Uanis(C19A) ~ Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C18') ~ Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C15) ~ Ueq, Uanis(C15') ~ Ueq: with sigma of 0.02 and sigma for terminal 
atoms of 0.02
4. others
 1-Sof(H19A)=1-Sof(H19A)=1-Sof(H19A)=1-Sof(H19A)=1-Sof(H19A)=1-Sof(H19A)=
 Sof(H18A)=Sof(H18B)=Sof(C19')=Sof(H19D)=Sof(H19E)=Sof(H19F)
5.a Ternary CH refined with riding coordinates:
 C2(H2A), C2'(H2'A), C3(H3), C3'(H3'), C7(H7), C7'(H7'), C8(H8), C8'(H8')
5.b Secondary CH2 refined with riding coordinates:
 C12(H12C,H12D), C12'(H12A,H12B), C13(H13C,H13D), C13'(H13A,H13B), C14(H14C,
 H14D), C14'(H14A,H14B), C16(H16C,H16D), C16'(H16A,H16B), C17(H17C,H17D),
 C17'(H17A,H17B), C18(H18E,H18F), C18'(H18C,H18D), C18'(H18A,H18B)
5.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N1'(H1'), N2(H2), N2'(H2')
5.d Idealised Me refined as rotating group:
 C19A(H19A,H19B,H19C), C4(H4A,H4B,H4C), C4'(H4'A,H4'B,H4'C), C5(H5A,H5B,H5C),
 C5'(H5'A,H5'B,H5'C), C9(H9A,H9B,H9C), C9'(H9'A,H9'B,H9'C), C10(H10D,H10E,H10F),
  C10'(H10A,H10B,H10C), C15(H15D,H15E,H15F), C15'(H15A,H15B,H15C), C19(H19G,
 H19H,H19I), C19'(H19D,H19E,H19F)
;