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_4033205
_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      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-06-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                96.813(3)
_cell_angle_beta                 93.134(3)
_cell_angle_gamma                107.521(3)
_cell_formula_units_Z            2
_cell_length_a                   9.2367(3)
_cell_length_b                   9.8868(3)
_cell_length_c                   14.3883(4)
_cell_measurement_reflns_used    7304
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.3230
_cell_measurement_theta_min      2.7760
_cell_volume                     1238.47(7)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 16.2096
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -77.00  -48.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2661 -178.0000  120.0000 29

  2 omega -101.00  -47.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2661  178.0000  120.0000 54

  3 omega  -40.00   46.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598  -57.0000  -90.0000 86

  4 omega   40.00   83.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598 -133.0000   82.4657 43

  5 omega    6.00   92.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598   57.0000  150.0000 86

  6 omega  -31.00   -2.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598  133.0000  151.0949 29

  7 omega  -11.00   93.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598   19.0000   90.0000 104

  8 omega  -51.00   -7.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2661  -57.0000  -60.0000 44

  9 omega  -46.00   41.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -24.2661   57.0000  150.0000 87

 10 omega   19.00   81.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598   57.0000  -60.0000 62

 11 omega   -4.00   51.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598   77.0000   60.0000 55

 12 omega  -43.00   63.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598  -19.0000  -30.0000 106

 13 omega   40.00   67.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598  -99.0000 -120.0000 27

 14 omega    8.00   62.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       25.3598   57.0000 -120.0000 54
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0573653000
_diffrn_orient_matrix_UB_12      0.0549335000
_diffrn_orient_matrix_UB_13      0.0294761000
_diffrn_orient_matrix_UB_21      0.0501616000
_diffrn_orient_matrix_UB_22      0.0035647000
_diffrn_orient_matrix_UB_23      -0.0358825000
_diffrn_orient_matrix_UB_31      -0.0271551000
_diffrn_orient_matrix_UB_32      0.0523999000
_diffrn_orient_matrix_UB_33      -0.0181973000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            21408
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         2.648
_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  0.98936
_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.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.509
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       tables
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.114
_refine_diff_density_min         -0.448
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         5663
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0649
_refine_ls_R_factor_gt           0.0528
_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^)+(0.0708P)^2^+1.3152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1385
_refine_ls_wR_factor_ref         0.1464
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4671
_reflns_number_total             5663
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02484_si_002.cif
_cod_data_source_block           nms7_RS_RS_6b
_cod_depositor_comments
'Adding full bibliography for 4033202--4033205.cif.'
_cod_database_code               4033205
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C25 H21 Cl F6 N2 O4'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.51
_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 Ternary CH refined with riding coordinates:
 C21(H21)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C9(H9), C20(H20), C16(H16), C4(H4), C6(H6), C17(H17), C18(H18),
 C19(H19), C7(H7)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              60694
_shelx_hkl_checksum              96472
_olex2_submission_special_instructions 'No special instructions were received'