Selective Formation of Functionalized α-Quaternary Malononitriles toward 5,5-Disubstituted Pyrrolopyrimidinones.
Whitehead, Alan; Zhang, Yong; McCabe Dunn, Jamie; Sherer, Edward C.; Lam, Yu-Hong; Stelmach, John; Sun, Aaron; Shiroda, Melisa; Orr, Robert K.; Waddell, Sherman T.; Raghavan, Subharekha; Organic letters 19 (2017) 4448–4451; doi:10.1021/acs.orglett.7b01930

data_1547006
_publ_section_title
;
 Selective Formation of Functionalized \a-Quaternary Malononitriles toward
 5,5-Disubstituted Pyrrolopyrimidinones.
;
_journal_issue                   17
_journal_name_full               'Organic letters'
_journal_page_first              4448
_journal_page_last               4451
_journal_paper_doi               10.1021/acs.orglett.7b01930
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H18 Cl F5 N6 O'
_chemical_formula_sum            'C24 H18 Cl F5 N6 O'
_chemical_formula_weight         536.884
_chemical_name_systematic
;
(S)-4-amino-2-(6-chloro-1-(3,3,4,4,4-pentafluorobutyl)
-1H-indazol-3-yl)-5-methyl-5-phenyl-5,7-dihydro
-6H-pyrrolo[2,3-d]pyrimidin-6-one
;
_space_group_IT_number           170
_symmetry_cell_setting           hexagonal
_symmetry_Int_Tables_number      170
_symmetry_space_group_name_Hall  'P 65'
_symmetry_space_group_name_H-M   'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.1
_audit_creation_date             2009-10-28
_audit_creation_method           'merge of exptl & shelxl CIFs via mrlcif'
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_formula_units_Z            6
_cell_length_a                   17.34103(12)
_cell_length_b                   17.34103(12)
_cell_length_c                   15.00551(10)
_cell_measurement_radiation      'Cu K\a'
_cell_measurement_reflns_used    26553
_cell_measurement_temperature    273
_cell_measurement_theta_max      66.2269
_cell_measurement_theta_min      2.9391
_cell_volume                     3907.79(5)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.48 (release 15-09-2009 CrysAlis171 .NET)
(compiled Sep 15 2009,11:49:04)
;
_computing_data_collection
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.48 (release 15-09-2009 CrysAlis171 .NET)
(compiled Sep 15 2009,11:49:04)
;
_computing_data_reduction
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.48 (release 15-09-2009 CrysAlis171 .NET)
(compiled Sep 15 2009,11:49:04)
;
_computing_molecular_graphics
;
ORTEP3 (Johnson,2000), PLATON (Spek,1990),
PSPLUTO (local version of Motherwell's program)
;
_computing_publication_material  'locally developed programs'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      273
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 10.4752
_diffrn_detector_type            'Oxford Diffraction Ruby CCD'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
datacollection start_time: 2009-Oct-20 18:11:25
1 omega  -98.00  -53.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -10.1429  179.0000 -180.0000 45
  2 omega  -97.00  -54.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
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  3 omega  -97.00  -60.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
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  4 omega  -29.00   14.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -10.1429  -38.0000 -120.0000 43
  5 omega  -23.00   61.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       10.1429   77.0000 -120.0000 84
  6 omega   43.00   95.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   15.0000  120.0000 52
  7 omega   66.00  163.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  150.0000 97
  8 omega   75.00  167.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  125.0000  -90.0000 92
  9 omega   25.00   67.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -113.0000   95.0000 42
 10 omega  122.00  148.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000 -180.0000 26
 11 omega   31.00   75.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -23.0000   39.0000 44
 12 omega  133.00  164.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   45.0000  -90.0000 31
 13 omega  100.00  126.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -15.0000  -90.0000 26
 14 omega  147.00  173.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   15.0000  120.0000 26
 15 omega   19.00   76.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000  -30.0000 57
 16 omega   58.00   84.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -51.0000   35.0000 26
 17 omega   66.00  123.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   45.0000   60.0000 57
 18 omega   39.00   65.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -77.0000  120.0000 26
 19 omega   33.00   77.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000 -150.0000 44
 20 omega   35.00   71.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000   60.0000 36
 21 omega   97.00  123.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -77.0000  -30.0000 26
 22 omega   26.00   91.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -58.0000  -87.0000 65
 23 omega   67.00  111.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   45.0000   90.0000 44
 24 omega   19.00   72.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000    0.0000 -180.0000 53
 25 omega  129.00  177.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000    0.0000 -180.0000 48
 26 omega   49.00   88.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -15.0000  -90.0000 39
 27 omega   34.00   67.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000 -113.0000  173.0000 33
 28 omega   65.00   97.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  -60.0000 32
 29 omega  119.00  159.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000   30.0000 40
 30 omega   38.00   69.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -77.0000 -150.0000 31
 31 omega  134.00  170.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000 -150.0000 36
 32 omega   52.00   77.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -45.0000 -120.0000 25
 33 omega   33.00   75.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000  -23.0000  156.0000 42
 34 omega   95.00  152.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   15.0000  -90.0000 57
 35 omega   93.00  176.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   15.0000 -120.0000 83
 36 omega  -87.00   16.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -10.1429  -36.0000  101.0000 103
 37 omega  -89.00   24.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -10.1429  -77.0000 -150.0000 113
 38 omega  -37.00   67.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -10.1429   33.0000 -176.0000 104
 39 omega  -16.00   86.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       10.1429   38.0000   90.0000 102
 40 omega  -23.00   54.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       10.1429 -102.0000   74.0000 77
 41 omega   59.00  133.00   1.0000  150.0000
omega____ theta____ kappa____ phi______ frames
    -       92.5000   77.0000  -30.0000 74
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Oxford Diffraction Gemini R Ultra'
_diffrn_measurement_method       'omega scans'
_diffrn_measurement_specimen_support 'microloop / oil'
_diffrn_orient_matrix_UB_11      -0.0676729701
_diffrn_orient_matrix_UB_12      0.0110003847
_diffrn_orient_matrix_UB_13      -0.0571615951
_diffrn_orient_matrix_UB_21      -0.0203266434
_diffrn_orient_matrix_UB_22      0.0429385102
_diffrn_orient_matrix_UB_23      0.0797732554
_diffrn_orient_matrix_UB_31      0.0743563773
_diffrn_orient_matrix_UB_32      0.0924915775
_diffrn_orient_matrix_UB_33      -0.0302049891
_diffrn_radiation_collimation    '300 micron, focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'Enhance Ultra (Cu) X-ray Source'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0402
_diffrn_reflns_av_sigmaI/netI    0.0649
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            46742
_diffrn_reflns_theta_full        66.34
_diffrn_reflns_theta_max         66.2269
_diffrn_reflns_theta_min         2.9391
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_power             40
_diffrn_source_size              '0.4 x 12 mm fine focus'
_diffrn_source_target            Cu
_diffrn_source_type              'Oxford Diffraction Enhance Ultra'
_diffrn_source_voltage           40
_exptl_absorpt_coefficient_mu    1.8795
_exptl_absorpt_correction_T_max  0.897
_exptl_absorpt_correction_T_min  0.800
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.48 (release 15-09-2009 CrysAlis171 .NET)
(compiled Sep 15 2009,11:49:04)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_density_method    none
_exptl_crystal_description       'faceted block'
_exptl_crystal_F_000             1644
_exptl_crystal_size_max          0.094
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.059
_refine_diff_density_max         0.201
_refine_diff_density_min         -0.167
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.004(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         4584
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0288
_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^)+(0.0586P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0757
_refine_ls_wR_factor_ref         0.0769
_reflns_number_gt                4209
_reflns_number_total             4584
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol7b01930_si_001.cif
_cod_data_source_block           mde120
_cod_depositor_comments
;
The following automatic conversions were performed:

'_symmetry_cell_setting' value 'Hexagonal' changed to 'hexagonal'
according to
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_database_code               1547006
_cell_oxdiff_angle_alpha         90.005(2)
_cell_oxdiff_angle_beta          89.991(2)
_cell_oxdiff_angle_gamma         120.004(3)
_cell_oxdiff_length_a            17.3512(5)
_cell_oxdiff_length_b            17.3354(5)
_cell_oxdiff_length_c            15.0022(5)
_cell_oxdiff_measurement_reflns_used 26553
_cell_oxdiff_volume              3907.79(19)
_diffrn_reflns_numb_unique_mrl   4584
_reflns_odcompleteness_completeness 99.55
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49