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_4033202
_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         'C20 H17 Cl N2 O4'
_chemical_formula_sum            'C20 H18 Cl N2 O4'
_chemical_formula_weight         385.81
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-06-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.118(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.3053(4)
_cell_length_b                   14.8181(5)
_cell_length_c                   8.1391(4)
_cell_measurement_reflns_used    2536
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.6190
_cell_measurement_theta_min      3.0280
_cell_volume                     1835.40(12)
_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, 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 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -93.00    7.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241  -77.0000  -90.0000 100

  2 omega  -82.00  -35.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241  -38.0000  -60.0000 47

  3 omega  -57.00  -32.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -22.4241  178.0000   60.0000 25

  4 omega  -22.00   54.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       23.3616  -99.0000   60.0000 76
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0282614000
_diffrn_orient_matrix_UB_12      0.0356392000
_diffrn_orient_matrix_UB_13      0.0188085000
_diffrn_orient_matrix_UB_21      -0.0333612000
_diffrn_orient_matrix_UB_22      -0.0317917000
_diffrn_orient_matrix_UB_23      0.0120038000
_diffrn_orient_matrix_UB_31      0.0161145000
_diffrn_orient_matrix_UB_32      -0.0033893000
_diffrn_orient_matrix_UB_33      0.0847553000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0233
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            8977
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         2.677
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.237
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93187
_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    1.396
_exptl_crystal_description       prizm
_exptl_crystal_F_000             804
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.633
_refine_diff_density_min         -0.734
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         4215
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0723
_refine_ls_R_factor_gt           0.0558
_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^)+(0.0414P)^2^+2.5713P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1223
_refine_ls_wR_factor_ref         0.1323
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3366
_reflns_number_total             4215
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02484_si_002.cif
_cod_data_source_block           rnv38_4q
_cod_depositor_comments
'Adding full bibliography for 4033202--4033205.cif.'
_cod_original_cell_volume        1835.39(12)
_cod_database_code               4033202
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'c20 h17 cl1 n2 o4'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.51
_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. Uiso/Uaniso restraints and constraints
Uanis(C15A) = Uanis(C16A) = Uanis(C17A) = Uanis(C18A) = Uanis(C19A) =
Uanis(C20A) = Uanis(C15) = Uanis(C16) = Uanis(C17) = Uanis(C18) = Uanis(C19) =
Uanis(C20)
3. Others
 Sof(C15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=
 Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=1-FVAR(1)
 Sof(C15)=Sof(C16)=Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=
 Sof(H19)=Sof(C20)=Sof(H20)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C9(H9), C7(H7), C3(H3), C4(H4), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A)
4.b Fitted hexagon refined as free rotating group:
 C15(C16,C17,C18,C19,C20), C15A(C16A,C17A,C18A,C19A,C20A)
4.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              48162
_shelx_hkl_checksum              75172
_olex2_submission_special_instructions 'No special instructions were received'