Palladium-Catalyzed Asymmetric Formal [3+2] Cycloaddition of α-N-Heterocyclic Acrylates with Vinyl Epoxides for Construction of Isonucleoside Analogs
Huang, Ke-Xin; Xie, Ming-Sheng; Wang, Dong-Chao; Sang, Ji-Wei; Qu, Gui-Rong; Guo, Hai-Ming; Chemical Communications  (2019) –; doi:10.1039/C9CC07571B

data_7124348
_publ_section_title
;
 Palladium-Catalyzed Asymmetric Formal [3+2] Cycloaddition of
 \a-N-Heterocyclic Acrylates with Vinyl Epoxides for Construction of
 Isonucleoside Analogs
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC07571B
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C15 H18 Cl N5 O3'
_chemical_formula_sum            'C15 H18 Cl N5 O3'
_chemical_formula_weight         351.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_symmetry_space_group_name_Hall  'I 2y'
_symmetry_space_group_name_H-M   'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-07-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-22 deposited with the CCDC.    2019-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.033(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5414(2)
_cell_length_b                   7.33570(10)
_cell_length_c                   19.5853(3)
_cell_measurement_reflns_used    2826
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4370
_cell_measurement_theta_min      4.5850
_cell_volume                     1632.82(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -28.00  69.00   1.00    1.00    --   40.98 -57.00  30.00   97
  2  \w     64.00  89.00   1.00    1.00    --   40.98-125.00 -90.00   25
  3  \w     70.00 116.00   1.00    1.00    --  106.95-125.00 -90.00   46
  4  \w     37.00 132.00   1.00    1.00    --  106.95 -45.00 -30.00   95
  5  \w     97.00 148.00   1.00    1.00    --  106.95  45.00 -60.00   51
  6  \w     96.00 121.00   1.00    1.00    --  106.95 125.00 -30.00   25
  7  \w    113.00 175.00   1.00    1.00    --  106.95 125.00  90.00   62
  8  \w    115.00 174.00   1.00    1.00    --  106.95  45.00 150.00   59
  9  \w     64.00 115.00   1.00    1.00    --   40.98  38.00 120.00   51
 10  \w     25.00 104.00   1.00    1.00    --  106.95 -95.00 150.00   79
 11  \w      1.00  50.00   1.00    1.00    --   40.98 -99.00   0.00   49
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0723969000
_diffrn_orient_matrix_UB_12      0.1741157000
_diffrn_orient_matrix_UB_13      0.0063222000
_diffrn_orient_matrix_UB_21      0.1087788000
_diffrn_orient_matrix_UB_22      0.1175667000
_diffrn_orient_matrix_UB_23      -0.0043921000
_diffrn_orient_matrix_UB_31      -0.0354821000
_diffrn_orient_matrix_UB_32      0.0076963000
_diffrn_orient_matrix_UB_33      -0.0795179000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0145
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            3141
_diffrn_reflns_point_group_measured_fraction_full 0.730
_diffrn_reflns_point_group_measured_fraction_max 0.701
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.533
_diffrn_reflns_theta_min         4.157
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.297
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93223
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.431
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 565 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.046(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         2300
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0264
_refine_ls_R_factor_gt           0.0263
_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^)+(0.0472P)^2^+0.5170P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0696
_refine_ls_wR_factor_ref         0.0696
_reflns_Friedel_coverage         0.333
_reflns_Friedel_fraction_full    0.414
_reflns_Friedel_fraction_max     0.381
_reflns_number_gt                2291
_reflns_number_total             2300
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07571b2.cif
_cod_data_source_block           2-cl
_cod_database_code               7124348
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C12(H12)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C11(H11A,H11B,H11C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.194
_oxdiff_exptl_absorpt_empirical_full_min 0.862