Enantioselective 1,3-Dipolar Cycloaddition of Methyleneindolinones with α-Diazomethylphosphonate to Access Chiral Spiro-phosphonylpyrazoline-oxindoles Catalyzed by Tertiary Amine Thiourea and 1,5-Diazabicyclo[4.3.0]non-5-ene.
Huang, Nan; Zou, Liangliang; Peng, Yungui; Organic letters 19 (2017) 5806–5809; doi:10.1021/acs.orglett.7b02763

data_1547729
_publ_section_title
;
 Enantioselective 1,3-Dipolar Cycloaddition of Methyleneindolinones with
 \a-Diazomethylphosphonate to Access Chiral
 Spiro-phosphonylpyrazoline-oxindoles Catalyzed by Tertiary Amine Thiourea
 and 1,5-Diazabicyclo[4.3.0]non-5-ene.
;
_journal_issue                   21
_journal_name_full               'Organic letters'
_journal_page_first              5806
_journal_page_last               5809
_journal_paper_doi               10.1021/acs.orglett.7b02763
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H18 N3 O4 P'
_chemical_formula_sum            'C18 H18 N3 O4 P'
_chemical_formula_weight         371.32
_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     iterative
_audit_creation_date             2017-03-31
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.0735(19)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.49772(17)
_cell_length_b                   7.06251(13)
_cell_length_c                   13.2196(2)
_cell_measurement_reflns_used    5929
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.9900
_cell_measurement_theta_min      4.7910
_cell_volume                     860.13(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -91.00  -3.00   1.00    1.00    --  -37.03 126.00-180.00   88
  2  \w   -104.00 -20.00   1.00    1.00    --  -37.03 -57.00  30.00   84
  3  \w      1.00  76.00   1.00    1.00    --   37.03 -99.00-150.00   75
  4  \w     20.00 104.00   1.00    1.00    --   37.03  57.00 -30.00   84
  5  \w     20.00 104.00   1.00    1.00    --   37.03  57.00  30.00   84
  6  \w     24.00  91.00   1.00    1.00    --   37.03-126.00  30.00   67
  7  \w    -31.00  64.00   1.00    1.00    --   37.03 -77.00-180.00   95
  8  \w     41.00 109.00   1.00    1.00    --  110.47 -95.00 120.00   68
  9  \w     89.00 178.00   1.00    1.00    --  110.47  30.00   0.00   89
 10  \w     43.00 137.00   1.00    1.00    --  110.47 -77.00-180.00   94
 11  \w     41.00 109.00   1.00    1.00    --  110.47 -95.00 150.00   68
 12  \w     41.00 132.00   1.00    1.00    --  110.47 -30.00 150.00   91
 13  \w     84.00 178.00   1.00    1.00    --  110.47  77.00 -60.00   94
 14  \w     57.00 151.00   1.00    1.00    --  110.47 178.00 120.00   94
 15  \w   -106.00 -18.00   1.00    1.00    --  -37.03 -38.00  90.00   88
 16  \w   -105.00 -10.00   1.00    1.00    --  -37.03 -77.00 -60.00   95
 17  \w   -105.00 -10.00   1.00    1.00    --  -37.03 -77.00-150.00   95
 18  \w    -31.00  64.00   1.00    1.00    --   37.03 -77.00  60.00   95
 19  \w    -32.00  56.00   1.00    1.00    --   37.03 -38.00 -90.00   88
 20  \w    -30.00  54.00   1.00    1.00    --   37.03 -57.00  60.00   84
 21  \w     93.00 178.00   1.00    1.00    --  110.47  45.00-120.00   85
 22  \w     89.00 178.00   1.00    1.00    --  110.47  30.00 150.00   89
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1131300000
_diffrn_orient_matrix_UB_12      -0.1533568000
_diffrn_orient_matrix_UB_13      -0.0449958000
_diffrn_orient_matrix_UB_21      0.1230999000
_diffrn_orient_matrix_UB_22      -0.1414455000
_diffrn_orient_matrix_UB_23      -0.0013944000
_diffrn_orient_matrix_UB_31      -0.0005144000
_diffrn_orient_matrix_UB_32      -0.0636604000
_diffrn_orient_matrix_UB_33      0.1113832000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            6718
_diffrn_reflns_point_group_measured_fraction_full 0.923
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.053
_diffrn_reflns_theta_min         3.447
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.685
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67535
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.434
_exptl_crystal_description       block
_exptl_crystal_F_000             388
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.384
_refine_diff_density_min         -0.351
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 1151 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.028(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.915
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         2874
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.914
_refine_ls_R_factor_all          0.0413
_refine_ls_R_factor_gt           0.0408
_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^)+(0.1000P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1081
_refine_ls_wR_factor_ref         0.1091
_reflns_Friedel_coverage         0.725
_reflns_Friedel_fraction_full    0.851
_reflns_Friedel_fraction_max     0.867
_reflns_number_gt                2815
_reflns_number_total             2874
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02763_si_002.cif
_cod_data_source_block           pyg-2017-3-29
_cod_depositor_comments          'Adding full bibliography for 1547729.cif.'
_cod_original_cell_volume        860.12(3)
_cod_database_code               1547729
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 O1 N1 P1'
_reflns_odcompleteness_completeness 100.00
_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.a Ternary CH refined with riding coordinates:
 C4(H4)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), N3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15),
 C16(H16), C17(H17)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.427
_oxdiff_exptl_absorpt_empirical_full_min 0.601