Tuning the Reactivity of Difluoromethyl Sulfoximines from Electrophilic to Nucleophilic: Stereoselective Nucleophilic Difluoromethylation of Aryl Ketones
Xiao Shen; Wei Zhang; Chuanfa Ni; Yucheng Gu; Jinbo Hu; Journal of the American Chemical Society 134 (2012) 16999–17002; doi:10.1021/ja308419a

data_4118781
_publ_section_title
;
 Tuning the Reactivity of Difluoromethyl Sulfoximines from Electrophilic
 to Nucleophilic: Stereoselective Nucleophilic Difluoromethylation of Aryl
 Ketones
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16999
_journal_page_last               17002
_journal_paper_doi               10.1021/ja308419a
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H12 Br F2 N O2 S'
_chemical_formula_sum            'C14 H12 Br F2 N O2 S'
_chemical_formula_weight         376.22
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_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_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.9675(12)
_cell_length_b                   10.996(2)
_cell_length_c                   22.753(5)
_cell_measurement_reflns_used    6119
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      66.94
_cell_measurement_theta_min      3.89
_cell_volume                     1493.0(5)
_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-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.950
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_sigmaI/netI    0.0319
_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       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            6688
_diffrn_reflns_theta_full        66.94
_diffrn_reflns_theta_max         66.94
_diffrn_reflns_theta_min         3.89
_exptl_absorpt_coefficient_mu    5.308
_exptl_absorpt_correction_T_max  0.6189
_exptl_absorpt_correction_T_min  0.1652
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.674
_exptl_crystal_description       column
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.53
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.750
_refine_diff_density_min         -0.481
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.06(3)
_refine_ls_extinction_coef       0.0049(3)
_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   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     195
_refine_ls_number_reflns         2488
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0337
_refine_ls_R_factor_gt           0.0333
_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^)+(0.0395P)^2^+1.1550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0901
_refine_ls_wR_factor_ref         0.0905
_reflns_number_gt                2449
_reflns_number_total             2488
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja308419a_si_003.cif
_cod_data_source_block           053
_cod_database_code               4118781