Synthesis of 1,2-Dihydropyrimidine-2-carboxylates via Regioselective Addition of Rhodium(II) Carbenoids to 2H-Azirine-2-carbaldimines.
Novikov, Mikhail S.; Rostovskii, Nikolai V.; Koronatov, Alexander N.; Zavyalov, Kirill V.; Zubakin, Grigory V.; Khlebnikov, Alexander F.; Starova, Galina L.; The Journal of organic chemistry 82 (2017) 13396–13404; doi:10.1021/acs.joc.7b02484

data_4033203
_publ_section_title
;
 Synthesis of 1,2-Dihydropyrimidine-2-carboxylates via Regioselective
 Addition of Rhodium(II) Carbenoids to 2H-Azirine-2-carbaldimines.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13396
_journal_page_last               13404
_journal_paper_doi               10.1021/acs.joc.7b02484
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C25 H21 Cl F6 N2 O4'
_chemical_formula_sum            'C25 H21 Cl F6 N2 O4'
_chemical_formula_weight         562.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-06-07
_audit_creation_method
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Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
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_cell_length_c                   11.6733(4)
_cell_measurement_reflns_used    6951
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.7190
_cell_measurement_theta_min      3.3330
_cell_volume                     2479.71(16)
_computing_cell_refinement
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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)
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_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)
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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)
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_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 16.2096
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_details
;
  1 omega  -86.00  -55.00   1.0000   43.4900
omega____ theta____ kappa____ phi______ frames
    -      -17.8777  178.0000  120.0000 31

  2 omega  -88.00  -48.00   1.0000   43.4900
omega____ theta____ kappa____ phi______ frames
    -      -17.8777 -178.0000 -150.0000 40

  3 omega   -4.00   88.00   1.0000   43.4900
omega____ theta____ kappa____ phi______ frames
    -       18.9714   38.0000 -180.0000 92

  4 omega    0.00   86.00   1.0000   43.4900
omega____ theta____ kappa____ phi______ frames
    -       18.9714   38.0000   90.0000 86

  5 omega   19.00   86.00   1.0000   43.4900
omega____ theta____ kappa____ phi______ frames
    -       18.9714   57.0000 -120.0000 67

  6 omega  -25.00   33.00   1.0000   43.4900
omega____ theta____ kappa____ phi______ frames
    -       18.9714  -99.0000  120.0000 58

  7 omega   60.00   88.00   1.0000   43.4900
omega____ theta____ kappa____ phi______ frames
    -       18.9714   57.0000  -90.0000 28
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_diffrn_measurement_device_type  'Xcalibur, Eos'
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_diffrn_orient_matrix_UB_12      -0.0024580000
_diffrn_orient_matrix_UB_13      -0.0266650000
_diffrn_orient_matrix_UB_21      0.0287080000
_diffrn_orient_matrix_UB_22      0.0297727000
_diffrn_orient_matrix_UB_23      0.0290519000
_diffrn_orient_matrix_UB_31      0.0443003000
_diffrn_orient_matrix_UB_32      -0.0168078000
_diffrn_orient_matrix_UB_33      0.0553066000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0251
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            19864
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.498
_diffrn_reflns_theta_min         2.771
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.235
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98610
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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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)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       prizm
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.405
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
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_refine_ls_hydrogen_treatment    constr
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_refine_ls_number_reflns         5571
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0505
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_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0266P)^2^+1.6789P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0793
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4631
_reflns_number_total             5571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02484_si_002.cif
_cod_data_source_block           endo-exo-5b
_cod_depositor_comments
'Adding full bibliography for 4033202--4033205.cif.'
_cod_original_cell_volume        2479.73(15)
_cod_database_code               4033203
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'c25 h21 n2 o4 f6 cl1'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Ternary CH refined with riding coordinates:
 C4(H4), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C19(H19), C17(H17), C20(H20), C6(H6), C18(H18), C10(H10), C9(H9),
 C16(H16)
2.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              58672
_shelx_hkl_checksum              63985
_olex2_submission_special_instructions 'No special instructions were received'