Asymmetric Mannich Reaction of Isatin-Based Ketimines with α-Diazomethylphosphonates Catalyzed by Chiral Silver Phosphate.
Chen, Jing; Wen, Xiaojing; Wang, Yan; Du, Fei; Cai, Liu; Peng, Yungui; Organic letters 18 (2016) 4336–4339; doi:10.1021/acs.orglett.6b02095

data_1543962
_publ_section_title
;
 Asymmetric Mannich Reaction of Isatin-Based Ketimines with
 \a-Diazomethylphosphonates Catalyzed by Chiral Silver Phosphate.
;
_journal_issue                   17
_journal_name_full               'Organic letters'
_journal_page_first              4336
_journal_page_last               4339
_journal_paper_doi               10.1021/acs.orglett.6b02095
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C17 H23 N4 O6 P'
_chemical_formula_sum            'C17 H23 N4 O6 P'
_chemical_formula_weight         410.36
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-03-26
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.23 svn.r2946 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.73106(13)
_cell_length_b                   10.22183(14)
_cell_length_c                   19.6704(2)
_cell_measurement_reflns_used    7018
_cell_measurement_temperature    279.66(10)
_cell_measurement_theta_max      71.3790
_cell_measurement_theta_min      4.8600
_cell_volume                     1956.60(4)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      279.66(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega  -31.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  -77.0000  -60.0000 94

  2 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  -57.0000  120.0000 84

  3 omega   55.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203 -178.0000 -120.0000 54

  4 omega   57.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  178.0000  -90.0000 52

  5 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  -57.0000    0.0000 84

  6 omega    1.00   76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  -99.0000   90.0000 75

  7 omega   38.00   91.00   1.0000    3.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 53

  8 omega   39.00  110.00   1.0000    3.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -95.0000 -120.0000 71

  9 omega   38.00  116.00   1.0000    3.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -112.0000  120.0000 78

 10 omega   38.00   91.00   1.0000    3.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 53

 11 omega   81.00  176.00   1.0000    3.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 95

 12 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   57.0000  -90.0000 84

 13 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   57.0000   60.0000 84

 14 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   57.0000    0.0000 84

 15 omega   57.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203  178.0000  -30.0000 52

 16 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7203   57.0000  150.0000 84

 17 omega   70.00  178.00   1.0000    3.3000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   60.0000 108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1574683000
_diffrn_orient_matrix_UB_12      -0.0152172000
_diffrn_orient_matrix_UB_13      0.0005296000
_diffrn_orient_matrix_UB_21      -0.0067297000
_diffrn_orient_matrix_UB_22      0.0527922000
_diffrn_orient_matrix_UB_23      -0.0732681000
_diffrn_orient_matrix_UB_31      0.0144004000
_diffrn_orient_matrix_UB_32      -0.1404284000
_diffrn_orient_matrix_UB_33      -0.0276097000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0281
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10421
_diffrn_reflns_point_group_measured_fraction_full 0.934
_diffrn_reflns_point_group_measured_fraction_max 0.906
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.507
_diffrn_reflns_theta_min         4.496
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.623
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53884
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.748
_refine_diff_density_min         -1.187
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 1231 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.036(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     278
_refine_ls_number_reflns         3449
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0623
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0720P)^2^+3.3990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1580
_refine_ls_wR_factor_ref         0.1605
_reflns_Friedel_coverage         0.604
_reflns_Friedel_fraction_full    0.844
_reflns_Friedel_fraction_max     0.799
_reflns_number_gt                3311
_reflns_number_total             3449
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b02095_si_002.cif
_cod_data_source_block           pyg-cj150207
_cod_depositor_comments          'Adding full bibliography for 1543962.cif.'
_cod_database_code               1543962
_shelxl_version_number           2014-1
_chemical_oxdiff_formula         'C1 H1 N1 O1 P1'
_reflns_odcompleteness_completeness 99.95
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C99B-O1B
 1.3 with sigma of 0.01
 C99B-P1B
 2.8 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(N2) \\sim Ueq, Uanis(C99B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C3A) = Uanis(O7A)
Uanis(C9) = Uanis(C6BA) = Uanis(N9AA)
Uanis(N2) = Uanis(N99A)
Uanis(C99B) = Uanis(N2)
Uanis(C99B) = Uanis(C99A)
Uanis(N2) = Uanis(N1)
4. Others
 Fixed Sof: N99A(0.5) P1A(0.5) O7A(0.5) O1A(0.5) C99A(0.5) H99A(0.5) H99B(0.5)
 H99C(0.5) N2(0.5) C3A(0.5) H3AA(0.5) H3AB(0.5) H3AC(0.5) P1B(0.5) O7B(0.5)
 N99B(0.5) O1B(0.5) N1(0.5) C99B(0.5) H99D(0.5) H99E(0.5) H99F(0.5) C3B(0.5)
 H3BA(0.5) H3BB(0.5) H3BC(0.5)
5.a Me refined with everything fixed:
 C99A(H99A,H99B,H99C), C3A(H3AA,H3AB,H3AC), C99B(H99D,H99E,H99F), C3B(H3BA,
 H3BB,H3BC)
5.b Aromatic/amide H refined with riding coordinates:
 C4AA(H4AA), C6AA(H6AA), N9AA(H9AA), C4(H4), C6(H6)
5.c Idealised Me refined as rotating group:
 C5AA(H5AA,H5AB,H5AC), C2BA(H2BA,H2BB,H2BC), C4BA(H4BA,H4BB,H4BC), C5(H5A,H5B,
 H5C)
;
_shelx_res_checksum              3959
_shelx_hkl_checksum              17565
_olex2_submission_special_instructions 'No special instructions were received'