Catalytic Asymmetric Intermolecular Stetter Reaction of Heterocyclic Aldehydes with Nitroalkenes: Backbone Fluorination Improves Selectivity
Daniel A. DiRocco; Kevin M. Oberg; Derek M. Dalton; Tomislav Rovis; Journal of the American Chemical Society 131 (2009) 10872–10874; doi:10.1021/ja904375q

data_4104853
_publ_section_title
;
 Catalytic Asymmetric Intermolecular Stetter Reaction of Heterocyclic
 Aldehydes with Nitroalkenes: Backbone Fluorination Improves Selectivity
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10872
_journal_page_last               10874
_journal_paper_doi               10.1021/ja904375q
_journal_volume                  131
_journal_year                    2009
_chemical_absolute_configuration syn
_chemical_formula_sum            'C14 H13 B F9 N3'
_chemical_formula_weight         405.08
_space_group_IT_number           4
_symmetry_cell_setting           monoclinic
_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_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 107.6080(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   9.9143(3)
_cell_length_b                   7.5803(2)
_cell_length_c                   11.2293(3)
_cell_measurement_reflns_used    6246
_cell_measurement_temperature    120
_cell_measurement_theta_max      33.11
_cell_measurement_theta_min      2.41
_cell_volume                     804.38(4)
_computing_cell_refinement       'APEX2 (Bruker, 2009)'
_computing_data_collection       'APEX2 (Bruker, 2009)'
_computing_data_reduction        'APEX2 (Bruker, 2009)'
_computing_molecular_graphics    'APEX2 (Bruker, 2009)'
_computing_publication_material  'APEX2 (Bruker, 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_sigmaI/netI    0.0650
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14071
_diffrn_reflns_theta_full        32.58
_diffrn_reflns_theta_max         32.58
_diffrn_reflns_theta_min         2.41
_exptl_absorpt_coefficient_mu    0.174
_exptl_absorpt_correction_T_max  0.9909
_exptl_absorpt_correction_T_min  0.9683
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Sheldrick, G. M. (2008) SADABS.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.672
_exptl_crystal_description       plate
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.1(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     246
_refine_ls_number_reflns         5310
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0464
_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^)+(0.0357P)^2^+0.0379P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0778
_refine_ls_wR_factor_ref         0.0906
_reflns_number_gt                3593
_reflns_number_total             5310
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja904375q_si_005.cif
_cod_data_source_block           rovis58_0m
_cod_database_code               4104853