Valence Tautomerism in Titanium Enolates: Catalytic Radical Haloalkylation and Application in the Total Synthesis of Neodysidenin
Stéphane Beaumont; Elizabeth A. Ilardi; Lucas R. Monroe; Armen Zakarian; Journal of the American Chemical Society 132 (2010) 1482–1483; doi:10.1021/ja910154f

data_4101874
_publ_section_title
;
 Valence Tautomerism in Titanium Enolates: Catalytic Radical
 Haloalkylation and Application in the Total Synthesis of Neodysidenin
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1482
_journal_page_last               1483
_journal_paper_doi               10.1021/ja910154f
_journal_volume                  132
_journal_year                    2010
_chemical_absolute_configuration ad
_chemical_formula_sum            'C11 H15 Cl6 N O3'
_chemical_formula_weight         421.94
_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                 98.187(9)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   5.887(4)
_cell_length_b                   11.304(7)
_cell_length_c                   13.230(8)
_cell_measurement_temperature    293(2)
_cell_volume                     871.4(10)
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'Omega scan'
_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  0.0574
_diffrn_reflns_av_sigmaI/netI    0.0615
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6504
_diffrn_reflns_theta_full        25.66
_diffrn_reflns_theta_max         25.66
_diffrn_reflns_theta_min         1.56
_exptl_absorpt_coefficient_mu    0.992
_exptl_absorpt_correction_T_max  0.319
_exptl_absorpt_correction_T_min  0.215
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'psi scan'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.608
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             428
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.248
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.05(8)
_refine_ls_extinction_coef       0.022(2)
_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   0.932
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     206
_refine_ls_number_reflns         3113
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.932
_refine_ls_R_factor_all          0.0550
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.100
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0474P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0858
_refine_ls_wR_factor_ref         0.0920
_reflns_number_gt                2448
_reflns_number_total             3113
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja910154f_si_004.cif
_cod_data_source_block           s112509
_cod_original_cell_volume        871.4(9)
_cod_database_code               4101874