Enantioselective Aza-Heck Cyclizations of N-(Tosyloxy)carbamates: Synthesis of Pyrrolidines and Piperidines.
Ma, Xiaofeng; Hazelden, Ian R.; Langer, Thomas; Munday, Rachel H.; Bower, John F.; Journal of the American Chemical Society 141 (2019) 3356–3360; doi:10.1021/jacs.8b12689

data_4127788
_publ_section_title
;
 Enantioselective Aza-Heck Cyclizations of N-(Tosyloxy)carbamates:
 Synthesis of Pyrrolidines and Piperidines.
;
_journal_issue                   8
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3356
_journal_page_last               3360
_journal_paper_doi               10.1021/jacs.8b12689
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H20 Br N O2 S'
_chemical_formula_sum            'C19 H20 Br N O2 S'
_chemical_formula_weight         406.33
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-06-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.544(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.8351(6)
_cell_length_b                   13.2300(10)
_cell_length_c                   8.4949(7)
_cell_measurement_reflns_used    9414
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.98
_cell_measurement_theta_min      2.40
_cell_volume                     879.70(12)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker Apex suite'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            16421
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.080
_diffrn_reflns_theta_min         2.400
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.466
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5551
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1164 before and 0.0321 after correction. The Ratio of minimum to maximum transmission is 0.7445. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.534
_exptl_crystal_description       block
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.44
_exptl_crystal_size_mid          0.382
_exptl_crystal_size_min          0.338
_refine_diff_density_max         0.443
_refine_diff_density_min         -0.243
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1923 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         4247
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0199
_refine_ls_R_factor_gt           0.0190
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0265P)^2^+0.1458P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0458
_refine_ls_wR_factor_ref         0.0461
_reflns_Friedel_coverage         0.915
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                4135
_reflns_number_total             4247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b12689_si_002.cif
_cod_data_source_block           testm1
_cod_database_code               4127788
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.489
_shelx_estimated_absorpt_t_min   0.410
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16),
 C18(H18), C19(H19)
2.c X=CH2 refined with riding coordinates:
 C6(H6A,H6B)
;
_shelx_res_checksum              12412
_shelx_hkl_checksum              39708
_olex2_submission_special_instructions 'No special instructions were received'