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_4028749
_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         'C18 H18 Cl N2 O4 P'
_chemical_formula_sum            'C18 H18 Cl N2 O4 P'
_chemical_formula_weight         392.76
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-10-12
_audit_creation_method
;
  Olex2 1.2
  (compiled 2012.05.09 svn.r2324, GUI svn.r4230)
;
_cell_angle_alpha                99.330(3)
_cell_angle_beta                 95.904(3)
_cell_angle_gamma                90.344(3)
_cell_formula_units_Z            4
_cell_length_a                   8.7196(3)
_cell_length_b                   12.0985(5)
_cell_length_c                   18.3711(6)
_cell_measurement_reflns_used    8147
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      66.9491
_cell_measurement_theta_min      3.7003
_cell_volume                     1901.75(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_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 0.9985
_diffrn_measurement_details
;
  1 omega  -69.00  -15.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -57.0000  120.0000 54

  2 omega    0.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000  120.0000 42

  3 omega  -36.00  -11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       18.0000  120.0000  128.7615 25

  4 omega  -23.00    2.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       34.0000  125.0000  102.9723 25

  5 omega   -9.00   16.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       38.0000  108.0000  -92.9378 25

  6 omega    2.00   28.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       42.0000   95.0000   91.7772 26

  7 omega  -46.00   30.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   30.0000   90.0000 76

  8 omega  -53.00   -1.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   61.0000  120.0000 52

  9 omega  -47.00   29.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000  -30.0000 76

 10 omega  -39.00   29.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -      -42.5000   37.0000 -180.0000 68

 11 omega -113.00  -50.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -      -42.5000 -162.0000  118.0000 63

 12 omega  -57.00  -12.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   60.0000 45

 13 omega -109.00  -63.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -      -42.5000  -77.0000   60.0000 46

 14 omega   19.00   45.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       46.0000   78.0000  -88.0983 26

 15 omega   47.00  107.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       46.0000   78.0000  -88.0983 60

 16 omega   17.00   42.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       50.0000   82.0000    3.7673 25

 17 omega   17.00   46.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       50.0000   82.0000 -130.6005 29

 18 omega   17.00   42.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       50.0000   83.0000  158.8513 25

 19 omega   15.00   40.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       50.0000   85.0000 -176.0703 25

 20 omega   18.00   44.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       50.0000   84.0000  -87.9405 26

 21 omega   21.00   46.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       54.0000   84.0000 -144.0829 25

 22 omega   22.00   47.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       54.0000   81.0000   31.5936 25

 23 omega   20.00   45.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       54.0000   84.0000  156.7203 25

 24 omega   21.00   46.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       54.0000   83.0000  -31.6567 25

 25 omega   22.00   47.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       54.0000   80.0000   47.6882 25

 26 omega   27.00  108.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       56.0000 -125.0000 -120.0000 81

 27 omega   94.00  120.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       56.0000  162.0000  145.0000 26

 28 omega   16.00   75.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000  -90.0000 59

 29 omega   29.00   99.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000   81.2033 70

 30 omega   30.00  126.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       58.0000   76.0000  157.0607 96

 31 omega   31.00  126.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       58.0000   71.0000  -19.4019 95

 32 omega   30.00  108.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       58.0000   73.0000 -138.2904 78

 33 omega   35.00   81.00   1.0000    1.2800
omega____ theta____ kappa____ phi______ frames
    -       62.0000   30.0000  101.3263 46

 34 omega   90.00  173.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -180.0000 83

 35 omega   84.00  109.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -30.0000 25

 36 omega   90.00  177.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000   30.0000 87

 37 omega   82.00  175.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000   60.0000 93

 38 omega   90.00  130.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  120.0000 40

 39 omega   90.00  166.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -30.0000 76

 40 omega   40.00   96.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  120.0000 56

 41 omega   82.00  108.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -180.0000 26

 42 omega  115.00  169.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000   90.0000 54

 43 omega   55.00  108.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000 -180.0000 53

 44 omega   82.00  111.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000   90.0000 29

 45 omega   82.00  107.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  150.0000 25

 46 omega   40.00   66.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000   30.0000 26

 47 omega  118.00  174.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -60.0000 56

 48 omega   82.00  108.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000    0.0000 26

 49 omega   82.00  115.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -60.0000 33

 50 omega   82.00  178.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -150.0000 96

 51 omega   83.00  109.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -30.0000 26

 52 omega   49.00  116.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  -60.0000 67

 53 omega   82.00  108.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000   30.0000 26

 54 omega   83.00  115.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -60.0000 32

 55 omega  123.00  159.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 36

 56 omega   82.00  107.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 25

 57 omega   84.00  110.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  -90.0000 26

 58 omega   90.00  117.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000 -150.0000 27

 59 omega   90.00  170.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  150.0000 80

 60 omega   41.00   98.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -45.0000  150.0000 57

 61 omega   91.00  117.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000    0.0000 26

 62 omega   90.00  117.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000   60.0000 27

 63 omega  113.00  178.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -90.0000 65

 64 omega   83.00  162.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000   30.0000 79

 65 omega   82.00  109.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -90.0000 27

 66 omega   49.00  107.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000  -30.0000 58

 67 omega   88.00  115.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   30.0000  120.0000 27

 68 omega  122.00  178.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  120.0000 56

 69 omega   90.00  121.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   61.0000  -90.0000 31

 70 omega   41.00   99.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -94.0000   60.0000 58

 71 omega   82.00  107.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  120.0000 25
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1446765000
_diffrn_orient_matrix_UB_12      -0.0153487000
_diffrn_orient_matrix_UB_13      -0.0566461000
_diffrn_orient_matrix_UB_21      0.1005994000
_diffrn_orient_matrix_UB_22      0.0119652000
_diffrn_orient_matrix_UB_23      -0.0626083000
_diffrn_orient_matrix_UB_31      0.0226829000
_diffrn_orient_matrix_UB_32      -0.1276008000
_diffrn_orient_matrix_UB_33      -0.0132006000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            26000
_diffrn_reflns_theta_full        67.06
_diffrn_reflns_theta_max         67.06
_diffrn_reflns_theta_min         3.70
_diffrn_source                   'Enhance (Cu) x-ray Source'
_diffrn_source_current           n/a
_diffrn_source_voltage           n/a
_exptl_absorpt_coefficient_mu    2.800
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63358
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.372
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.232
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.001(11)
_refine_ls_extinction_coef       0.00247(14)
_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   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     954
_refine_ls_number_reflns         12135
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0474
_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^)+(0.0987P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1334
_refine_ls_wR_factor_ref         0.1625
_reflns_number_gt                6154
_reflns_number_total             12135
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo4018342_si_002_2.cif
_cod_data_source_block           201210178a
_cod_original_cell_volume        1901.74(11)
_cod_database_code               4028749
_chemical_oxdiff_formula         C20H20N4O4P1Cl1
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97