Enantioselective Synthesis of 1,2-Diamines Containing Tertiary and Quaternary Centers through Rhodium-Catalyzed DYKAT of Racemic Allylic Trichloroacetimidates.
Mwenda, Edward T.; Nguyen, Hien M.; Organic letters 19 (2017) 4814–4817; doi:10.1021/acs.orglett.7b02256

data_1547588
_publ_section_title
;
 Enantioselective Synthesis of 1,2-Diamines Containing Tertiary and
 Quaternary Centers through Rhodium-Catalyzed DYKAT of Racemic Allylic
 Trichloroacetimidates.
;
_journal_issue                   18
_journal_name_full               'Organic letters'
_journal_page_first              4814
_journal_page_last               4817
_journal_paper_doi               10.1021/acs.orglett.7b02256
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_sum            'C21 H26 N2 O3 S'
_chemical_formula_weight         386.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 99.675(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.3983(6)
_cell_length_b                   8.7684(9)
_cell_length_c                   17.9628(18)
_cell_measurement_reflns_used    6133
_cell_measurement_temperature    190(2)
_cell_measurement_theta_max      25.6
_cell_measurement_theta_min      2.3
_cell_volume                     993.43(17)
_computing_cell_refinement       'APEXII (Bruker-AXS,2015)'
_computing_data_collection       'APEXII (Bruker-AXS,2015)'
_computing_data_reduction        'APEXII (Bruker-AXS,2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'Shelxt, APEXII (Bruker-AXS,2015)'
_diffrn_ambient_temperature      190(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker Nonius KappaCCD-ApexII'
_diffrn_measurement_method       'CCD phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            15946
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.995
_diffrn_reflns_theta_min         2.592
_exptl_absorpt_coefficient_mu    0.187
_exptl_absorpt_correction_type   multi-scans
_exptl_absorpt_process_details   'SADABS APEXII (Bruker-AXS, 2015)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.292
_exptl_crystal_description       plate
_exptl_crystal_F_000             412
_exptl_crystal_size_max          0.390
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.080
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1832 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).

 The conformation of the N1 to C5 ring is disordered and associated 
 with disorder in the C7-C8 double bond. The relative occupancy
 refined to 0.731(8) for part1 and 0.269(8) for part2 (the 
 primed labels). The N1, C2, C3, C4, C5 ring is a C3 envelope
 and the N1, C2', C3', C4', C5' ring is a C4' envelope. Associated
 with change in the 5-member ring conformation is an ~145 degree
 rotation about the C6-(double bond centroid) direction.
 
 The anisotropic displacement parameters for partial atoms in close
 proximity ( <0.3A) were constrained to be the same (C2' C2'; C5,C5', 
 C6, C6'). The anisotropic displacement parameters for N1 > N9 
 (this includes both disordered parts) were restrained with the
 rigid bond restraint. The bond distances of the two disordered
 parts were restrained to be the same (e.g. N1-C2 = N1-C2';
 C2-C3 = C2'-C3', etc.)

;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         5261
_refine_ls_number_restraints     130
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0355
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+0.0504P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0818
_refine_ls_wR_factor_ref         0.0871
_reflns_Friedel_coverage         0.879
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                4552
_reflns_number_total             5261
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02256_si_002.cif
_cod_data_source_block           ngu171
_cod_database_code               1547588
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.931
_shelx_estimated_absorpt_t_max   0.985
_shelx_res_checksum              60795
_shelx_hkl_checksum              85561