Construction of Vicinal Tetrasubstituted Stereocenters with a C-F Bond through a Catalytic Enantioselective Detrifluoroacetylative Mannich Reaction.
Liu, Xihong; Zhang, Jinlong; Zhao, Long; Ma, Shixiong; Yang, Dongxu; Yan, Wenjin; Wang, Rui; The Journal of organic chemistry 80 (2015) 12651–12658; doi:10.1021/acs.joc.5b02238

data_4036498
_publ_section_title
;
 Construction of Vicinal Tetrasubstituted Stereocenters with a C-F Bond
 through a Catalytic Enantioselective Detrifluoroacetylative Mannich
 Reaction.
;
_journal_issue                   24
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12651
_journal_page_last               12658
_journal_paper_doi               10.1021/acs.joc.5b02238
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C30 H27 Br F N2 O4'
_chemical_formula_sum            'C30 H27 Br F N O5'
_chemical_formula_weight         580.43
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2015-07-01
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.755(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4818(7)
_cell_length_b                   8.7184(4)
_cell_length_c                   23.3607(11)
_cell_measurement_reflns_used    2031
_cell_measurement_temperature    293.33(10)
_cell_measurement_theta_max      19.6590
_cell_measurement_theta_min      3.7700
_cell_volume                     2809.0(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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_environment      air
_diffrn_ambient_temperature      293.33(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details
;
  1 omega    3.00   54.00   0.7500    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.4291   77.0000  -30.0000 68

  2 omega   -9.00   44.25   0.7500    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.4291   77.0000   90.0000 71

  3 omega   12.00   63.00   0.7500    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.4291   77.0000 -120.0000 68

  4 omega   55.00   82.00   0.7500    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854   77.0000   30.0000 36

  5 omega   52.00   90.25   0.7500    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854   77.0000  -30.0000 51

  6 omega   42.00   72.00   0.7500    4.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854   77.0000   90.0000 40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0329057000
_diffrn_orient_matrix_UB_12      -0.0624099000
_diffrn_orient_matrix_UB_13      -0.0047224000
_diffrn_orient_matrix_UB_21      0.0377326000
_diffrn_orient_matrix_UB_22      -0.0479844000
_diffrn_orient_matrix_UB_23      0.0173866000
_diffrn_orient_matrix_UB_31      -0.0118221000
_diffrn_orient_matrix_UB_32      0.0205202000
_diffrn_orient_matrix_UB_33      0.0262970000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.1416
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            12872
_diffrn_reflns_point_group_measured_fraction_full 0.860
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.022
_diffrn_reflns_theta_min         3.365
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.509
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52937
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.372
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1192
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.27
_refine_diff_density_max         0.224
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1099 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.016(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.884
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     727
_refine_ls_number_reflns         9428
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      0.894
_refine_ls_R_factor_all          0.1663
_refine_ls_R_factor_gt           0.0589
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0580P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1110
_refine_ls_wR_factor_ref         0.1663
_reflns_Friedel_coverage         0.651
_reflns_Friedel_fraction_full    0.731
_reflns_Friedel_fraction_max     0.724
_reflns_number_gt                4323
_reflns_number_total             9428
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b02238_si_002.cif
_cod_data_source_block           liuxh0629
_cod_database_code               4036498
_reflns_odcompleteness_completeness 96.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C39) \\sim Ueq, Uanis(C39') \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C54) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C55') \\sim Ueq, Uanis(C54')
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C40) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C60) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: H53(0.6) H53A(0.4) H40C(0.5) H40D(0.5) H40A(0.5) H40B(0.5)
 C54(0.6) H54(0.6) O9(0.5) O9'(0.5) C54'(0.4) H54'(0.4) C55'(0.4) H55'(0.4)
 C55(0.6) H55(0.6) C39'(0.5) H39A(0.5) H39B(0.5) C39(0.5) H39C(0.5) H39D(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C19(H19A,H19B), C8(H8A,H8B), C49(H49A,H49B), C40(H40C,H40D),
 C40(H40A,H40B), C39'(H39A,H39B), C39(H39C,H39D)
4.b Aromatic/amide H refined with riding coordinates:
 C46(H46), C21(H21), C15(H15), C44(H44), C18(H18), C43(H43), C22(H22),
 C16(H16), C36(H36), C34(H34), C23(H23), C35(H35), C53(H53), C53(H53A), C4(H4),
 C3(H3), C5(H5), C6(H6), C52(H52), C25(H25), C24(H24), C51(H51), C37(H37),
 C54(H54), C54'(H54'), C55'(H55'), C55(H55)
4.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C58(H58A,H58B,H58C)
;
_shelx_res_checksum              5051
_shelx_hkl_checksum              26711
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-06-29
_olex2_submission_special_instructions 'No special instructions were received'