Stereoselective Synthesis of Chiral β-Fluoro α-Amino Acids via Pd(II)-Catalyzed Fluorination of Unactivated Methylene C(sp(3))-H Bonds: Scope and Mechanistic Studies.
Zhang, Qi; Yin, Xue-Song; Chen, Kai; Zhang, Shuo-Qing; Shi, Bing-Feng; Journal of the American Chemical Society 137 (2015) 8219–8226; doi:10.1021/jacs.5b03989

data_4123894
_publ_section_title
;
 Stereoselective Synthesis of Chiral \b-Fluoro \a-Amino Acids via
 Pd(II)-Catalyzed Fluorination of Unactivated Methylene C(sp(3))-H Bonds:
 Scope and Mechanistic Studies.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8219
_journal_page_last               8226
_journal_paper_doi               10.1021/jacs.5b03989
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C26 H24 F N3 O3'
_chemical_formula_sum            'C26 H24 F N3 O3'
_chemical_formula_weight         445.48
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-05-29
_audit_creation_method
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Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 104.752(8)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.1939(8)
_cell_length_b                   14.0887(9)
_cell_length_c                   13.9512(13)
_cell_measurement_reflns_used    2628
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.2435
_cell_measurement_theta_min      2.8858
_cell_volume                     2317.8(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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      293.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0302701000
_diffrn_orient_matrix_UB_12      -0.0413999000
_diffrn_orient_matrix_UB_13      -0.0202665000
_diffrn_orient_matrix_UB_21      -0.0103722000
_diffrn_orient_matrix_UB_22      -0.0103779000
_diffrn_orient_matrix_UB_23      0.0466583000
_diffrn_orient_matrix_UB_31      -0.0509421000
_diffrn_orient_matrix_UB_32      0.0266992000
_diffrn_orient_matrix_UB_33      -0.0132474000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0345
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            10223
_diffrn_reflns_theta_full        25.35
_diffrn_reflns_theta_max         25.35
_diffrn_reflns_theta_min         2.89
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86313
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.43
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.161
_refine_diff_density_min         -0.166
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.004
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         4410
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0431
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0531P)^2^+0.0580P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.1064
_reflns_number_gt                3211
_reflns_number_total             4410
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5b03989_si_003.cif
_cod_data_source_block           150528_zq_8_115_12
_cod_database_code               4123894
_chemical_oxdiff_formula         'c10 h10 n2 o8 F1'
_reflns_odcompleteness_completeness 99.56
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C35(H35), C36(H36)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C1(H1), C2(H2A), C3(H3), C4(H4), C12(H12), C13(H13), C15(H15),
 C16(H16), C21(H21), C22(H22), C23(H23), C24(H24), N5(H5), C28(H28), C29(H29),
 C30(H30), C31(H31), C38(H38), C39(H39), C41(H41), C42(H42), C47(H47), C48(H48),
  C49(H49), C50(H50)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C43(H43A,H43B,
 H43C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C)
;