Regio- and Enantioselective Synthesis of Chiral Pyrimidine Acyclic Nucleosides via Rhodium-Catalyzed Asymmetric Allylation of Pyrimidines.
Liang, Lei; Xie, Ming-Sheng; Qin, Tao; Zhu, Man; Qu, Gui-Rong; Guo, Hai-Ming; Organic letters 19 (2017) 5212–5215; doi:10.1021/acs.orglett.7b02482

data_1547163
_publ_section_title
;
 Regio- and Enantioselective Synthesis of Chiral Pyrimidine Acyclic
 Nucleosides via Rhodium-Catalyzed Asymmetric Allylation of Pyrimidines.
;
_journal_issue                   19
_journal_name_full               'Organic letters'
_journal_page_first              5212
_journal_page_last               5215
_journal_paper_doi               10.1021/acs.orglett.7b02482
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H17 I N2 O3'
_chemical_formula_sum            'C21 H17 I N2 O3'
_chemical_formula_weight         472.26
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.6528(2)
_cell_length_b                   12.1548(2)
_cell_length_c                   21.7284(5)
_cell_measurement_reflns_used    18079
_cell_measurement_temperature    297.5(6)
_cell_measurement_theta_max      71.5900
_cell_measurement_theta_min      4.0540
_cell_volume                     2021.14(8)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297.5(6)
_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 0.996
_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    -53.00  31.00   0.80    2.96    --  -36.07  57.00-180.00  105
  2  \w    -31.00  61.80   0.80    2.96    --   36.07 -77.00 -60.00  116
  3  \w     23.00  87.80   0.80    2.96    --   36.07-125.00-120.00   81
  4  \w     19.00 103.00   0.80    2.96    --   36.07  57.00  90.00  105
  5  \w     17.00 105.00   0.80    2.96    --   36.07  38.00  60.00  110
  6  \w      1.00  73.80   0.80    2.96    --   36.07 -99.00  90.00   91
  7  \w     23.00  87.80   0.80    2.96    --   36.07-125.00 150.00   81
  8  \w    -31.00  53.00   0.80    2.96    --   36.07 -57.00  30.00  105
  9  \w    -31.00  53.00   0.80    2.96    --   36.07 -57.00   0.00  105
 10  \w     92.00 176.80   0.80   13.00    --  109.31  45.00-120.00  106
 11  \w     40.00 108.00   0.80   13.00    --  109.31 -95.00 -90.00   85
 12  \w     57.00 149.80   0.80   13.00    --  109.31 178.00 150.00  116
 13  \w     41.00 125.80   0.80   13.00    --  109.31 -45.00   0.00  106
 14  \w     39.00 131.00   0.80   13.00    --  109.31 -30.00 -90.00  115
 15  \w     40.00 108.00   0.80   13.00    --  109.31 -95.00-180.00   85
 16  \w     83.00 175.80   0.80   13.00    --  109.31  77.00  90.00  116
 17  \w     92.00 176.80   0.80   13.00    --  109.31  45.00 150.00  106
 18  \w   -104.00 -10.40   0.80    2.96    --  -36.07 -77.00 -30.00  117
 19  \w    -24.00  64.00   0.80    2.96    --   36.07 -80.00-117.00  110
 20  \w      9.00 102.60   0.80    2.96    --   36.07  77.00-150.00  117
 21  \w    -35.00  65.00   0.80    2.96    --   36.07 -19.00  90.00  125
 22  \w      9.00 102.60   0.80    2.96    --   36.07  77.00 120.00  117
 23  \w     19.00 103.00   0.80    2.96    --   36.07  57.00 -90.00  105
 24  \w      9.00 102.60   0.80    2.96    --   36.07  77.00 -90.00  117
 25  \w     19.00 103.00   0.80    2.96    --   36.07  57.00-180.00  105
 26  \w     83.00 175.80   0.80   13.00    --  109.31  77.00 -90.00  116
 27  \w     40.00 108.00   0.80   13.00    --  109.31 -95.00  90.00   85
 28  \w     88.00 176.80   0.80   13.00    --  109.31  30.00-150.00  111
 29  \w     88.00 176.80   0.80   13.00    --  109.31  30.00  60.00  111
 30  \w     91.00 175.00   0.80   13.00    --  109.31  61.00 -60.00  105
 31  \w     41.00 125.80   0.80   13.00    --  109.31 -45.00 150.00  106
 32  \w     92.00 176.80   0.80   13.00    --  109.31  45.00   0.00  106
 33  \w     83.00 175.80   0.80   13.00    --  109.31  77.00  60.00  116
 34  \w      9.00 102.60   0.80    2.96    --   36.07  77.00 -60.00  117
 35  \w     23.00  87.80   0.80    2.96    --   36.07-125.00-150.00   81
 36  \w      9.00 102.60   0.80    2.96    --   36.07  77.00   0.00  117
 37  \w     19.00 103.00   0.80    2.96    --   36.07  57.00  60.00  105
 38  \w     17.00 105.00   0.80    2.96    --   36.07  38.00-180.00  110
 39  \w      1.00  73.80   0.80    2.96    --   36.07 -99.00 -60.00   91
 40  \w      9.00 102.60   0.80    2.96    --   36.07  77.00  90.00  117
 41  \w    -31.00  61.80   0.80    2.96    --   36.07 -77.00 -30.00  116
 42  \w     91.00 175.00   0.80   13.00    --  109.31  61.00 120.00  105
 43  \w     83.00 175.80   0.80   13.00    --  109.31  77.00 150.00  116
 44  \w     83.00 175.80   0.80   13.00    --  109.31  77.00   0.00  116
 45  \w     40.00 108.00   0.80   13.00    --  109.31 -95.00   0.00   85
 46  \w     83.00 175.80   0.80   13.00    --  109.31  77.00-120.00  116
 47  \w     88.00 176.80   0.80   13.00    --  109.31  30.00-120.00  111
 48  \w     92.00 176.80   0.80   13.00    --  109.31  45.00 -30.00  106
 49  \w     92.00 176.80   0.80   13.00    --  109.31  45.00  60.00  106
 50  \w   -104.00 -10.40   0.80    2.96    --  -36.07 -77.00 120.00  117
 51  \w      7.00 107.00   0.80    2.96    --   36.07  19.00  90.00  125
 52  \w     19.00  74.20   0.80    2.96    --   36.07  57.00 120.00   69
 53  \w     19.00 103.00   0.80    2.96    --   36.07  57.00 -30.00  105
 54  \w     17.00 105.00   0.80    2.96    --   36.07  38.00 -90.00  110
 55  \w     19.00 103.00   0.80    2.96    --   36.07  57.00 -60.00  105
 56  \w     17.00 105.00   0.80    2.96    --   36.07  38.00-150.00  110
 57  \w    -31.00  53.00   0.80    2.96    --   36.07 -57.00  60.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0696818000
_diffrn_orient_matrix_UB_12      0.0618428000
_diffrn_orient_matrix_UB_13      -0.0568027000
_diffrn_orient_matrix_UB_21      0.0750140000
_diffrn_orient_matrix_UB_22      -0.0902936000
_diffrn_orient_matrix_UB_23      -0.0421661000
_diffrn_orient_matrix_UB_31      -0.1733024000
_diffrn_orient_matrix_UB_32      -0.0639916000
_diffrn_orient_matrix_UB_33      0.0045761000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0592
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            41231
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.773
_diffrn_reflns_theta_min         4.069
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.638
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.11736
_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            colorless
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_description       block
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1332 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.025(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     253
_refine_ls_number_reflns         4002
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0340
_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^)+(0.0418P)^2^+0.2322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0822
_refine_ls_wR_factor_ref         0.0843
_reflns_Friedel_coverage         0.735
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                3670
_reflns_number_total             4002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02482_si_002.cif
_cod_data_source_block           lll-1
_cod_depositor_comments          'Adding full bibliography for 1547163.cif.'
_cod_database_code               1547163
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C1 H1 O1 N1 I1'
_shelx_estimated_absorpt_t_max   0.312
_shelx_estimated_absorpt_t_min   0.187
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C5(H5), C2(H2), C3(H3), C20(H20), C18(H18), C4(H4), C14(H14),
 C15(H15), C17(H17), C16(H16)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_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 7.028
_oxdiff_exptl_absorpt_empirical_full_min 0.555