Regioselective Synthesis of 7-(Trimethylsilylethynyl)pyrazolo[1,5-a]pyrimidines via Reaction of Pyrazolamines with Enynones.
Golubev, Pavel; Karpova, Ekaterina A.; Pankova, Alena S.; Sorokina, Mariia; Kuznetsov, Mikhail A.; The Journal of organic chemistry 81 (2016) 11268–11275; doi:10.1021/acs.joc.6b02217

data_4037405
_publ_section_title
;
 Regioselective Synthesis of
 7-(Trimethylsilylethynyl)pyrazolo[1,5-a]pyrimidines via Reaction of
 Pyrazolamines with Enynones.
;
_journal_issue                   22
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11268
_journal_page_last               11275
_journal_paper_doi               10.1021/acs.joc.6b02217
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C23 H19 Cl N4 O2 Si'
_chemical_formula_sum            'C23 H19 Cl N4 O2 Si'
_chemical_formula_weight         446.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-07
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.329(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.9864(6)
_cell_length_b                   30.542(2)
_cell_length_c                   11.0261(8)
_cell_measurement_reflns_used    4723
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.3510
_cell_measurement_theta_min      3.1610
_cell_volume                     2257.8(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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_temperature      100(2)
_diffrn_detector_area_resol_mean 16.2096
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -88.00  -62.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917  -77.0000  150.0000 26

  2 omega  -41.00   49.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917   57.0000  -90.0000 90

  3 omega  -77.00  -50.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917 -178.0000  -60.0000 27

  4 omega  -27.00    9.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917  -77.0000  150.0000 36

  5 omega  -14.00   22.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917  -99.0000   30.0000 36

  6 omega  -40.00   49.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917   57.0000   30.0000 89

  7 omega  -36.00   48.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917   57.0000  150.0000 84

  8 omega  -21.00    7.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4917  -99.0000  -60.0000 28

  9 omega   51.00   82.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       20.4292  178.0000   30.0000 31

 10 omega  -16.00   10.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       20.4292  -99.0000  120.0000 26
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0366632000
_diffrn_orient_matrix_UB_12      0.0156046000
_diffrn_orient_matrix_UB_13      -0.0486794000
_diffrn_orient_matrix_UB_21      -0.0242307000
_diffrn_orient_matrix_UB_22      0.0143355000
_diffrn_orient_matrix_UB_23      0.0441097000
_diffrn_orient_matrix_UB_31      0.0961952000
_diffrn_orient_matrix_UB_32      0.0095386000
_diffrn_orient_matrix_UB_33      0.0133189000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0175
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10094
_diffrn_reflns_point_group_measured_fraction_full 0.903
_diffrn_reflns_point_group_measured_fraction_max 0.898
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.495
_diffrn_reflns_theta_min         3.111
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.249
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'translucent colorless'
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       prism
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.214
_refine_diff_density_min         -0.177
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 1625 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.884
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         4196
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      0.884
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0339
_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          0.1052
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.792
_reflns_Friedel_fraction_full    0.806
_reflns_Friedel_fraction_max     0.797
_reflns_number_gt                3970
_reflns_number_total             4196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02217_si_002.cif
_cod_data_source_block           1
_cod_database_code               4037405
_chemical_oxdiff_formula         'Si6 C20 Cl N5'
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C21(H21),
 C22(H22), C24(H24), C27(H27)
2.b Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'