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_4106200
_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 rm
_chemical_formula_moiety         'C22 H29 Br N2 O2'
_chemical_formula_sum            'C22 H29 Br N2 O2'
_chemical_formula_weight         433.38
_chemical_name_common            C22H29BrN2O2
_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                   7.1862(3)
_cell_length_b                   11.0021(5)
_cell_length_c                   27.7885(13)
_cell_measurement_reflns_used    5196
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      17.74
_cell_measurement_theta_min      2.36
_cell_volume                     2197.05(17)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0612
_diffrn_reflns_av_sigmaI/netI    0.0511
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            35706
_diffrn_reflns_theta_full        25.41
_diffrn_reflns_theta_max         25.41
_diffrn_reflns_theta_min         1.47
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.889
_exptl_absorpt_correction_T_max  0.8636
_exptl_absorpt_correction_T_min  0.7648
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2.10 (Sheldrick, 2004)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       needle
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.815
_refine_diff_density_min         -0.539
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.006(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         4033
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1181
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0743P)^2^+1.8745P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1446
_refine_ls_wR_factor_ref         0.1776
_reflns_number_gt                2219
_reflns_number_total             4033
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            ja202267k_si_003.cif
_cod_data_source_block           dp283
_cod_database_code               4106200