Regioselective Asymmetric α,α-Bisalkylation of Ketones via Complex-Induced Syn-Deprotonation of Chiral N-Amino Cyclic Carbamate Hydrazones
Sarah E. Wengryniuk; Daniel Lim; Don M. Coltart; Journal of the American Chemical Society 133 (2011) 8714–8720; doi:10.1021/ja202267k

data_4106201
_publ_section_title
;
 Regioselective Asymmetric \a,\a-Bisalkylation of Ketones via
 Complex-Induced Syn-Deprotonation of Chiral N-Amino Cyclic Carbamate
 Hydrazones
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8714
_journal_page_last               8720
_journal_paper_doi               10.1021/ja202267k
_journal_volume                  133
_journal_year                    2011
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C23 H29 Br N2 O2'
_chemical_formula_sum            'C23 H29 Br N2 O2'
_chemical_formula_weight         445.39
_chemical_name_common            C23H29BrN2O2
_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                   6.735(1)
_cell_length_b                   10.415(2)
_cell_length_c                   31.635(4)
_cell_measurement_reflns_used    5232
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      21.95
_cell_measurement_theta_min      2.57
_cell_volume                     2219.0(6)
_computing_cell_refinement       SAINT
_computing_data_collection       'Apex II 2.0 Rev.2 (Bruker, 2005)'
_computing_data_reduction        'SAINT 7.12A (Bruker, 2004)'
_computing_molecular_graphics    'SHELXTL 5.1, XP (Sheldrick, 1994)'
_computing_publication_material  'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      298(2)
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker Kappa Apex II'
_diffrn_measurement_method       \w
_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  0.0363
_diffrn_reflns_av_sigmaI/netI    0.0333
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            38041
_diffrn_reflns_theta_full        26.46
_diffrn_reflns_theta_max         26.46
_diffrn_reflns_theta_min         2.34
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.872
_exptl_absorpt_correction_T_max  0.7140
_exptl_absorpt_correction_T_min  0.4545
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2.10 (Sheldrick, 2004)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_description       Needles
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.351
_refine_diff_density_min         -0.306
_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   0.011(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         4567
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0357
_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^)+(0.0353P)^2^+0.4950P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0805
_refine_ls_wR_factor_ref         0.0878
_reflns_number_gt                3492
_reflns_number_total             4567
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja202267k_si_004.cif
_cod_data_source_block           dp309
_cod_database_code               4106201