Highly Enantioselective Acylation of Acyclic Meso 1,3-Diols through Synergistic Isothiourea-Catalyzed Desymmetrization/Chiroablative Kinetic Resolution.
Merad, Jérémy; Borkar, Prashant; Bouyon Yenda, Tracy; Roux, Christèle; Pons, Jean-Marc; Parrain, Jean-Luc; Chuzel, Olivier; Bressy, Cyril; Organic letters 17 (2015) 2118–2121; doi:10.1021/acs.orglett.5b00707

data_1520299
_publ_section_title
;
 Highly Enantioselective Acylation of Acyclic Meso 1,3-Diols through
 Synergistic Isothiourea-Catalyzed Desymmetrization/Chiroablative Kinetic
 Resolution.
;
_journal_issue                   9
_journal_name_full               'Organic letters'
_journal_page_first              2118
_journal_page_last               2121
_journal_paper_doi               10.1021/acs.orglett.5b00707
_journal_volume                  17
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H23 I O3'
_chemical_formula_sum            'C22 H23 I O3'
_chemical_formula_weight         462.30
_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'
_atom_sites_solution_hydrogens   geom
_audit_creation_date
;
'Mon Oct 13 21:06:21 2014'
;
_audit_creation_method
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_cell_angle_alpha                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   5.7232(4)
_cell_length_b                   10.8546(10)
_cell_length_c                   32.913(2)
_cell_measurement_reflns_used    4222
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.7190
_cell_measurement_theta_min      4.2890
_cell_volume                     2044.7(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3048
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
  1 omega -102.00  -76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.2867 -125.0000 -150.0000 26

  2 omega -126.00  -84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.2867  -99.0000  -90.0000 42

  3 omega -127.00  -90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.2867  -99.0000  -60.0000 37

  4 omega   24.00   83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       38.2867 -125.0000 -180.0000 59

  5 omega   35.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       38.2867   57.0000   90.0000 78

  6 omega   13.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       38.2867  -77.0000  -90.0000 45

  7 omega   37.00   98.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  -45.0000  -30.0000 61

  8 omega   28.00   85.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  -45.0000   90.0000 57

  9 omega  110.00  140.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  111.0000  150.0000 30

 10 omega   41.00  107.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  -94.0000  -60.0000 66

 11 omega   96.00  171.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698   61.0000   60.0000 75

 12 omega  121.00  161.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  111.0000  -60.0000 40

 13 omega   30.00   87.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  -45.0000 -180.0000 57

 14 omega  153.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  111.0000  150.0000 25

 15 omega   25.00   78.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      110.4698  -94.0000 -150.0000 53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1328601000
_diffrn_orient_matrix_UB_12      0.0702598000
_diffrn_orient_matrix_UB_13      -0.0334550000
_diffrn_orient_matrix_UB_21      -0.0469296000
_diffrn_orient_matrix_UB_22      -0.1063150000
_diffrn_orient_matrix_UB_23      -0.0299277000
_diffrn_orient_matrix_UB_31      -0.2293829000
_diffrn_orient_matrix_UB_32      0.0623955000
_diffrn_orient_matrix_UB_33      -0.0133398000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0621
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            7013
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.378
_diffrn_reflns_theta_min         4.289
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.443
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48010
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.502
_exptl_crystal_description
;
;
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.628
_refine_diff_density_min         -2.076
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details
;
 Flack x determined using 1147 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.125
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3929
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.125
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0594
_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^)+(0.0597P)^2^+9.0318P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1674
_refine_ls_wR_factor_ref         0.1916
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_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                3291
_reflns_number_total             3929
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5b00707_si_003.cif
_cod_data_source_block           jm3075
_cod_original_cell_volume        2044.6(3)
_cod_database_code               1520299
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.68
_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:
 C1(H1), C3(H3), C4(H4), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15),
 C16(H16), C17(H17), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_olex2_submission_special_instructions 'No special instructions were received'