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_7124347
_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         'C20 H19 Br N2 O6'
_chemical_formula_sum            'C20 H19 Br N2 O6'
_chemical_formula_weight         463.28
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-02-06
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.01.22 svn.r3481 for OlexSys, GUI svn.r5467)
;
_audit_update_record
;
2019-07-09 deposited with the CCDC.    2019-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.74390(10)
_cell_length_b                   12.3456(2)
_cell_length_c                   18.3547(3)
_cell_measurement_reflns_used    16821
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.4850
_cell_measurement_theta_min      4.2810
_cell_volume                     1981.37(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0528
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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   -103.00 -19.00   1.00    1.00    --  -36.21 -57.00 -60.00   84
  2  \w      1.00  75.00   1.00    1.00    --   36.21 -99.00 150.00   74
  3  \w    -35.00  66.00   1.00    1.00    --   36.21 -19.00 -90.00  101
  4  \w     19.00 103.00   1.00    1.00    --   36.21  57.00  90.00   84
  5  \w    -31.00  63.00   1.00    1.00    --   36.21 -77.00 -60.00   94
  6  \w    -31.00  53.00   1.00    1.00    --   36.21 -57.00-139.00   84
  7  \w     16.00 103.00   1.00    1.00    --   36.21  66.00-159.00   87
  8  \w     88.00 178.00   1.00    1.42    --  109.31  30.00 150.00   90
  9  \w     89.00 176.00   1.00    1.42    --  109.31  66.00-159.00   87
 10  \w     40.00 109.00   1.00    1.42    --  109.31 -95.00 150.00   69
 11  \w     40.00 109.00   1.00    1.42    --  109.31 -95.00  60.00   69
 12  \w     40.00 109.00   1.00    1.42    --  109.31 -95.00-150.00   69
 13  \w     41.00 127.00   1.00    1.42    --  109.31 -45.00 150.00   86
 14  \w     40.00 109.00   1.00    1.42    --  109.31 -95.00  30.00   69
 15  \w     40.00 109.00   1.00    1.42    --  109.31 -95.00 -60.00   69
 16  \w     88.00 178.00   1.00    1.42    --  109.31  30.00  60.00   90
 17  \w    -53.00  31.00   1.00    1.00    --  -36.21  57.00  90.00   84
 18  \w    -31.00  53.00   1.00    1.00    --   36.21 -57.00 120.00   84
 19  \w     19.00 103.00   1.00    1.00    --   36.21  57.00 150.00   84
 20  \w      9.00 104.00   1.00    1.00    --   36.21  77.00   0.00   95
 21  \w     23.00  90.00   1.00    1.00    --   36.21-125.00  60.00   67
 22  \w      9.00 104.00   1.00    1.00    --   36.21  77.00 -90.00   95
 23  \w    -30.00  57.00   1.00    1.00    --   36.21 -66.00  66.00   87
 24  \w     17.00 105.00   1.00    1.00    --   36.21  38.00  30.00   88
 25  \w     83.00 177.00   1.00    1.42    --  109.31  77.00 -60.00   94
 26  \w     83.00 177.00   1.00    1.42    --  109.31  77.00 150.00   94
 27  \w     92.00 178.00   1.00    1.42    --  109.31  45.00   0.00   86
 28  \w     83.00 177.00   1.00    1.42    --  109.31  77.00  90.00   94
 29  \w     83.00 177.00   1.00    1.42    --  109.31  77.00-120.00   94
 30  \w     88.00 178.00   1.00    1.42    --  109.31  30.00  90.00   90
 31  \w     71.00 178.00   1.00    1.42    --  109.31  15.00 -30.00  107
 32  \w     91.00 176.00   1.00    1.42    --  109.31  61.00-180.00   85
 33  \w   -104.00  -9.00   1.00    1.00    --  -36.21 -77.00  90.00   95
 34  \w      9.00 104.00   1.00    1.00    --   36.21  77.00-150.00   95
 35  \w      9.00 104.00   1.00    1.00    --   36.21  77.00  90.00   95
 36  \w     23.00  90.00   1.00    1.00    --   36.21-125.00 -60.00   67
 37  \w     17.00 105.00   1.00    1.00    --   36.21  38.00-180.00   88
 38  \w    -31.00  63.00   1.00    1.00    --   36.21 -77.00  30.00   94
 39  \w     23.00  90.00   1.00    1.00    --   36.21-125.00-150.00   67
 40  \w      7.00 108.00   1.00    1.00    --   36.21  19.00  30.00  101
 41  \w     83.00 177.00   1.00    1.42    --  109.31  77.00-150.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1432631000
_diffrn_orient_matrix_UB_12      0.0656133000
_diffrn_orient_matrix_UB_13      0.0211870000
_diffrn_orient_matrix_UB_21      0.0965781000
_diffrn_orient_matrix_UB_22      -0.0678466000
_diffrn_orient_matrix_UB_23      -0.0532844000
_diffrn_orient_matrix_UB_31      -0.0344924000
_diffrn_orient_matrix_UB_32      0.0816976000
_diffrn_orient_matrix_UB_33      -0.0612522000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0324
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            29703
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.666
_diffrn_reflns_theta_min         4.316
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.186
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21153
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.553
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.285
_refine_diff_density_min         -0.481
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1567 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.034(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3907
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0262
_refine_ls_R_factor_gt           0.0253
_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^)+(0.0324P)^2^+0.3982P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0650
_refine_ls_wR_factor_ref         0.0657
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                3792
_reflns_number_total             3907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc07571b2.cif
_cod_data_source_block           hkx-20180205
_cod_database_code               7124347
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C1 O1 N1 Br1'
_shelx_estimated_absorpt_t_max   0.785
_shelx_estimated_absorpt_t_min   0.377
_reflns_odcompleteness_completeness 99.95
_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:
 C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b), C11(H11a,H11b)
2.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C2(H2), C28(H28), C16(H16), C27(H27), C25(H25)
2.d Idealised Me refined as rotating group:
 C14(H14a,H14b,H14c), C22(H22a,H22b,H22c)
;
_shelx_res_checksum              69052
_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 3.806
_oxdiff_exptl_absorpt_empirical_full_min 0.603