Synthesis of Chiral Acyclic Nucleosides by Sharpless Asymmetric Dihydroxylation: Access to Cidofovir and Buciclovir.
Qin, Tao; Li, Jian-Ping; Xie, Ming-Sheng; Qu, Gui-Rong; Guo, Hai-Ming; The Journal of organic chemistry 83 (2018) 15512–15523; doi:10.1021/acs.joc.8b02442

data_4034714
_publ_section_title
;
 Synthesis of Chiral Acyclic Nucleosides by Sharpless Asymmetric
 Dihydroxylation: Access to Cidofovir and Buciclovir.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              15512
_journal_page_last               15523
_journal_paper_doi               10.1021/acs.joc.8b02442
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H19 N2 O5'
_chemical_formula_sum            'C21 H19 N2 O5'
_chemical_formula_weight         379.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-07-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.9110(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.81390(10)
_cell_length_b                   13.3695(2)
_cell_length_c                   12.32600(10)
_cell_measurement_reflns_used    13740
_cell_measurement_temperature    297.01(10)
_cell_measurement_theta_max      72.4900
_cell_measurement_theta_min      4.8490
_cell_volume                     957.55(2)
_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)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297.01(10)
_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   -107.00  -7.00   1.00    1.00    --  -36.07 -19.00-150.00  100
  2  \w     19.00 103.00   1.00    1.00    --   36.07  57.00-120.00   84
  3  \w    -31.00  53.00   1.00    1.00    --   36.07 -57.00  30.00   84
  4  \w     17.00 105.00   1.00    1.00    --   36.07  38.00 -30.00   88
  5  \w    -31.00  63.00   1.00    1.00    --   36.07 -77.00   0.00   94
  6  \w     17.00 105.00   1.00    1.00    --   36.07  38.00-150.00   88
  7  \w     23.00  89.00   1.00    1.00    --   36.07-125.00-150.00   66
  8  \w    -31.00  53.00   1.00    1.00    --   36.07 -57.00  60.00   84
  9  \w     19.00 103.00   1.00    1.00    --   36.07  57.00  30.00   84
 10  \w      4.00  76.00   1.00    1.00    --   36.07-101.00 101.00   72
 11  \w    -31.00  53.00   1.00    1.00    --   36.07 -57.00 120.00   84
 12  \w    100.00 178.00   1.00    4.00    --  109.31 111.00  90.00   78
 13  \w     88.00 178.00   1.00    4.00    --  109.31  30.00 -60.00   90
 14  \w    100.00 178.00   1.00    4.00    --  109.31 111.00-150.00   78
 15  \w     40.00 109.00   1.00    4.00    --  109.31 -95.00 150.00   69
 16  \w     88.00 178.00   1.00    4.00    --  109.31  30.00  60.00   90
 17  \w     91.00 176.00   1.00    4.00    --  109.31  61.00 -30.00   85
 18  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 -90.00   94
 19  \w     42.00 136.00   1.00    4.00    --  109.31 -77.00-180.00   94
 20  \w     38.00 148.00   1.00    4.00    --  109.31 -15.00   0.00  110
 21  \w     41.00 127.00   1.00    4.00    --  109.31 -45.00-180.00   86
 22  \w     40.00 109.00   1.00    4.00    --  109.31 -95.00  60.00   69
 23  \w     40.00 109.00   1.00    4.00    --  109.31 -95.00 -30.00   69
 24  \w    100.00 178.00   1.00    4.00    --  109.31 111.00  60.00   78
 25  \w     39.00 131.00   1.00    4.00    --  109.31 -30.00  90.00   92
 26  \w     39.00 116.00   1.00    4.00    --  109.31-111.00-120.00   77
 27  \w     41.00 127.00   1.00    4.00    --  109.31 -45.00 -60.00   86
 28  \w     19.00 103.00   1.00    1.00    --   36.07  57.00 150.00   84
 29  \w     23.00  89.00   1.00    1.00    --   36.07-125.00 -30.00   66
 30  \w     23.00  89.00   1.00    1.00    --   36.07-125.00  60.00   66
 31  \w     19.00 103.00   1.00    1.00    --   36.07  57.00 120.00   84
 32  \w      9.00 104.00   1.00    1.00    --   36.07  77.00 -60.00   95
 33  \w      9.00 104.00   1.00    1.00    --   36.07  77.00-150.00   95
 34  \w    -31.00  53.00   1.00    1.00    --   36.07 -57.00-120.00   84
 35  \w      7.00 107.00   1.00    1.00    --   36.07  19.00 -90.00  100
 36  \w      9.00 104.00   1.00    1.00    --   36.07  77.00 150.00   95
 37  \w      9.00 104.00   1.00    1.00    --   36.07  77.00 -30.00   95
 38  \w    -33.00  55.00   1.00    1.00    --   36.07 -38.00 150.00   88
 39  \w      9.00 104.00   1.00    1.00    --   36.07  77.00  30.00   95
 40  \w     92.00 178.00   1.00    4.00    --  109.31  45.00  90.00   86
 41  \w     88.00 178.00   1.00    4.00    --  109.31  30.00-120.00   90
 42  \w     71.00 178.00   1.00    4.00    --  109.31  15.00-180.00  107
 43  \w     83.00 177.00   1.00    4.00    --  109.31  77.00-120.00   94
 44  \w     83.00 177.00   1.00    4.00    --  109.31  77.00  90.00   94
 45  \w     91.00 176.00   1.00    4.00    --  109.31  61.00  60.00   85
 46  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 -60.00   94
 47  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 120.00   94
 48  \w     88.00 178.00   1.00    4.00    --  109.31  30.00 -90.00   90
 49  \w     83.00 177.00   1.00    4.00    --  109.31  77.00 150.00   94
 50  \w     88.00 178.00   1.00    4.00    --  109.31  30.00-150.00   90
 51  \w     88.00 178.00   1.00    4.00    --  109.31  30.00  30.00   90
 52  \w   -103.00 -19.00   1.00    1.00    --  -36.07 -57.00  60.00   84
 53  \w     17.00 105.00   1.00    1.00    --   36.07  38.00 150.00   88
 54  \w     17.00  93.00   1.00    1.00    --   36.07  38.00  90.00   76
 55  \w      1.00  75.00   1.00    1.00    --   36.07 -99.00-180.00   74
 56  \w     19.00 103.00   1.00    1.00    --   36.07  57.00  90.00   84
 57  \w     17.00 105.00   1.00    1.00    --   36.07  38.00  30.00   88
 58  \w      9.00 104.00   1.00    1.00    --   36.07  77.00-120.00   95
 59  \w      1.00  75.00   1.00    1.00    --   36.07 -99.00 -60.00   74
;
_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      -0.0900874000
_diffrn_orient_matrix_UB_12      0.0979987000
_diffrn_orient_matrix_UB_13      0.0487575000
_diffrn_orient_matrix_UB_21      -0.0130578000
_diffrn_orient_matrix_UB_22      -0.0509612000
_diffrn_orient_matrix_UB_23      0.1117208000
_diffrn_orient_matrix_UB_31      0.2490198000
_diffrn_orient_matrix_UB_32      0.0327800000
_diffrn_orient_matrix_UB_33      0.0279627000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0415
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            20929
_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         72.579
_diffrn_reflns_theta_min         3.588
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.787
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.11619
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             398
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.384
_refine_diff_density_min         -0.244
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1510 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         3755
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0664P)^2^+0.0547P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1028
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.901
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                3486
_reflns_number_total             3755
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02442_si_002.cif
_cod_data_source_block           qt
_cod_database_code               4034714
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C1 H1 O1'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.744
_reflns_odcompleteness_completeness 99.94
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C4(H4), C18(H18), C28(H28), C24(H24), C26(H26), C27(H27), C25(H25),
 C19(H19), C22(H22), C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
2.d Idealised tetrahedral OH refined as rotating group:
 O13(H13), O12(H12)
;
_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 5.480
_oxdiff_exptl_absorpt_empirical_full_min 0.594