Rh(II)-Catalyzed Ring Expansion of Pyrazoles with Diazocarbonyl Compounds as a Method for the Preparation of 1,2-Dihydropyrimidines.
Koronatov, Alexander N.; Rostovskii, Nikolai V.; Khlebnikov, Alexander F.; Novikov, Mikhail S.; The Journal of organic chemistry 83 (2018) 9210–9219; doi:10.1021/acs.joc.8b01228

data_4035288
_publ_section_title
;
 Rh(II)-Catalyzed Ring Expansion of Pyrazoles with Diazocarbonyl Compounds
 as a Method for the Preparation of 1,2-Dihydropyrimidines.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9210
_journal_page_last               9219
_journal_paper_doi               10.1021/acs.joc.8b01228
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C20 H17 F3 N2 O2'
_chemical_formula_sum            'C20 H17 F3 N2 O2'
_chemical_formula_weight         374.35
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-12-27
_audit_creation_method
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Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                89.277(6)
_cell_angle_beta                 80.133(6)
_cell_angle_gamma                68.721(8)
_cell_formula_units_Z            2
_cell_length_a                   8.1579(7)
_cell_length_b                   9.1776(8)
_cell_length_c                   12.6068(7)
_cell_measurement_reflns_used    2823
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.2760
_cell_measurement_theta_min      3.1400
_cell_volume                     865.25(13)
_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
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
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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, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 16.2096
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega  -92.00   -7.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.5803  -77.0000   30.0000 85

  2 omega  -95.00   39.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.5803    0.0000   30.0000 134

  3 omega   63.00   88.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       23.5178 -178.0000  120.0000 25

  4 omega   13.00   65.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       23.5178  -99.0000  -60.0000 52

  5 omega    7.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       23.5178 -101.0000  150.0000 59

  6 omega   17.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       23.5178   57.0000 -120.0000 65
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0062844000
_diffrn_orient_matrix_UB_12      0.0350115000
_diffrn_orient_matrix_UB_13      -0.0503666000
_diffrn_orient_matrix_UB_21      0.0886565000
_diffrn_orient_matrix_UB_22      -0.0508118000
_diffrn_orient_matrix_UB_23      -0.0209394000
_diffrn_orient_matrix_UB_31      -0.0330928000
_diffrn_orient_matrix_UB_32      -0.0556026000
_diffrn_orient_matrix_UB_33      -0.0171930000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0411
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            7263
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.498
_diffrn_reflns_theta_min         2.822
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.115
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87745
_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            colorless
_exptl_crystal_density_diffrn    1.437
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       tables
_exptl_crystal_F_000             388
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.427
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3960
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0479
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0419P)^2^+0.3436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0949
_refine_ls_wR_factor_ref         0.1025
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3391
_reflns_number_total             3960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01228_si_002.cif
_cod_data_source_block           renv41
_cod_database_code               4035288
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C2 f3 o2 h170 N2'
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.51
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C16(H16), C20(H20), C19(H19), C10(H10), C2(H2), C18(H18), C17(H17),
 C4(H4), C6(H6), C7(H7), C9(H9)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_shelx_res_checksum              7788
_shelx_hkl_checksum              77116
_olex2_submission_special_instructions 'No special instructions were received'