Enantioselective Synthesis of Dialkylated α-Hydroxy Carboxylic Acids through Asymmetric Phase-Transfer Catalysis.
Duan, Shaobo; Li, Sanliang; Ye, Xinyi; Du, Nuan-Nuan; Tan, Choon-Hong; Jiang, Zhiyong; The Journal of organic chemistry 80 (2015) 7770–7778; doi:10.1021/acs.joc.5b01081

data_4031282
_publ_section_title
;
 Enantioselective Synthesis of Dialkylated \a-Hydroxy Carboxylic Acids
 through Asymmetric Phase-Transfer Catalysis.
;
_journal_issue                   15
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7770
_journal_page_last               7778
_journal_paper_doi               10.1021/acs.joc.5b01081
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H32 Br2 N3 O, Br'
_chemical_formula_sum            'C24 H32 Br3 N3 O'
_chemical_formula_weight         618.26
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.25 svn.r3098 for OlexSys, GUI svn.r4957)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.1655(3)
_cell_length_b                   15.7026(5)
_cell_length_c                   20.6676(10)
_cell_measurement_reflns_used    4807
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      72.2120
_cell_measurement_theta_min      4.2780
_cell_volume                     2649.99(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      291.15
_diffrn_detector_area_resol_mean 16.2312
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -19.00   19.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000   30.0000 38

  2 omega   12.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000 -180.0000 56

  3 omega  -28.00    8.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000 -180.0000 36

  4 omega   75.00  126.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000  120.0000 51

  5 omega   44.00  114.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000  -30.0000 70

  6 omega   34.00  121.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000   90.0000 87

  7 omega   29.00   90.00   1.0000    1.2000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000 -120.0000 61

  8 omega  102.00  133.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -60.0000 31

  9 omega   87.00  156.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  150.0000 69

 10 omega  137.00  175.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  120.0000 38

 11 omega  103.00  171.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -150.0000 68

 12 omega   92.00  173.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000 -120.0000 81

 13 omega   91.00  178.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000  -90.0000 87

 14 omega   94.00  177.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   77.0000   30.0000 83
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0751216000
_diffrn_orient_matrix_UB_12      0.0898370000
_diffrn_orient_matrix_UB_13      0.0050297000
_diffrn_orient_matrix_UB_21      0.1141384000
_diffrn_orient_matrix_UB_22      0.0204317000
_diffrn_orient_matrix_UB_23      0.0572428000
_diffrn_orient_matrix_UB_31      0.1300568000
_diffrn_orient_matrix_UB_32      0.0339254000
_diffrn_orient_matrix_UB_33      -0.0474057000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0238
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            9159
_diffrn_reflns_theta_full        67.07
_diffrn_reflns_theta_max         67.07
_diffrn_reflns_theta_min         3.53
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.796
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85635
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.550
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1240
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.425
_refine_diff_density_min         -0.405
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_coef       0.00237(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         4734
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0330
_refine_ls_R_factor_gt           0.0305
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0352P)^2^+0.6322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0740
_refine_ls_wR_factor_ref         0.0758
_reflns_number_gt                4472
_reflns_number_total             4734
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5b01081_si_002.cif
_cod_data_source_block           dscatbr
_cod_depositor_comments
'Adding full bibliography for 4031281--4031282.cif.'
_cod_original_cell_volume        2649.99(19)
_cod_database_code               4031282
_chemical_oxdiff_formula         C20H20N4O4Br1
_reflns_odcompleteness_completeness 99.93
_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. Restrained distances
 H2-N2
 0.82 with sigma of 0.02
 N1-H1
 0.82 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O1) \\sim Ueq, Uanis(Br2) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C8(H8)
4.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,
 H17B), C18(H18A,H18B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1A), C3(H3), C5(H5), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
4.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_olex2_submission_special_instructions 'No special instructions were received'