Detrifluoroacetylative in Situ Generation of Free 3-Fluoroindolin-2-one-Derived Tertiary Enolates: Design, Synthesis, and Assessment of Reactivity toward Asymmetric Mannich Reactions.
Xie, Chen; Zhang, Lijun; Sha, Wanxing; Soloshonok, Vadim A.; Han, Jianlin; Pan, Yi; Organic letters 18 (2016) 3270–3273; doi:10.1021/acs.orglett.6b01516

data_1543437
_publ_section_title
;
 Detrifluoroacetylative in Situ Generation of Free
 3-Fluoroindolin-2-one-Derived Tertiary Enolates: Design, Synthesis, and
 Assessment of Reactivity toward Asymmetric Mannich Reactions.
;
_journal_issue                   13
_journal_name_full               'Organic letters'
_journal_page_first              3270
_journal_page_last               3273
_journal_paper_doi               10.1021/acs.orglett.6b01516
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_sum            'C21 H23 F4 N2 O2 S'
_chemical_formula_weight         443.47
_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
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 107.206(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.501(2)
_cell_length_b                   8.8433(14)
_cell_length_c                   17.883(3)
_cell_measurement_reflns_used    4003
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.81
_cell_measurement_theta_min      2.38
_cell_volume                     2190.6(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0522
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12321
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        25.010
_diffrn_reflns_theta_max         25.010
_diffrn_reflns_theta_min         1.192
_exptl_absorpt_coefficient_mu    0.200
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.345
_exptl_crystal_description       block
_exptl_crystal_F_000             924
_exptl_crystal_size_max          0.280
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.220
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 2158 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     547
_refine_ls_number_reflns         7497
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0657
_refine_ls_R_factor_gt           0.0487
_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^)+(0.0737P)^2^+0.2334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1231
_refine_ls_wR_factor_ref         0.1361
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    0.938
_reflns_Friedel_fraction_max     0.938
_reflns_number_gt                5942
_reflns_number_total             7497
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b01516_si_002.cif
_cod_data_source_block           20160222pyxc1_0m_a
_cod_depositor_comments          'Adding full bibliography for 1543437.cif.'
_cod_original_cell_volume        2190.7(6)
_cod_database_code               1543437
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.946
_shelx_estimated_absorpt_t_max   0.957
_shelx_res_checksum              8757
_shelx_hkl_checksum              61562