TMSOTf Mediated ‘5/6-endo-dig’ Reductive Hydroamination for the Stereoselective Synthesis of Pyrrolidine and Piperidine derivatives
Gharpure, Santosh J.; Vishwakarma, Dharmendra S.; Patel, Raj Kumar; Chemical Communications  (2019) –; doi:10.1039/C9CC03127H

data_7123489
_publ_section_title
;
 TMSOTf Mediated &#x2018;5/6-endo-dig&#x2019; Reductive Hydroamination for
 the Stereoselective Synthesis of Pyrrolidine and Piperidine derivatives
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03127H
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C19 H23 N O2 S'
_chemical_formula_sum            'C19 H23 N O2 S'
_chemical_formula_weight         329.44
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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     dual
_audit_creation_date             2018-10-18
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-04-02 deposited with the CCDC.    2019-05-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.6838(3)
_cell_length_b                   11.6378(7)
_cell_length_c                   19.1666(13)
_cell_measurement_reflns_used    5820
_cell_measurement_temperature    150
_cell_measurement_theta_max      31.0500
_cell_measurement_theta_min      2.0800
_cell_volume                     1713.93(17)
_computing_cell_refinement       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_collection       'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_computing_data_reduction        'CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -75.50  19.00   0.50    8.00    --  -20.00 -72.00  36.00  189
  2  \w    -90.00   0.00   0.50    8.00    --  -20.00 -72.00-108.00  180
  3  \w    -30.00   0.00   0.50    8.00    --  -20.00   0.00-180.00   60
  4  \w    -96.50 -70.50   0.50    8.00    --  -20.00 -72.00 -36.00   52
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0295014000
_diffrn_orient_matrix_UB_12      0.0199231000
_diffrn_orient_matrix_UB_13      -0.0329338000
_diffrn_orient_matrix_UB_21      0.0870950000
_diffrn_orient_matrix_UB_22      0.0013608000
_diffrn_orient_matrix_UB_23      -0.0122672000
_diffrn_orient_matrix_UB_31      -0.0081513000
_diffrn_orient_matrix_UB_32      -0.0575574000
_diffrn_orient_matrix_UB_33      -0.0116362000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0392
_diffrn_reflns_av_unetI/netI     0.0458
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            7840
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        24.993
_diffrn_reflns_theta_max         24.993
_diffrn_reflns_theta_min         2.047
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.198
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88590
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.399
_refine_diff_density_min         -0.735
_refine_diff_density_rms         0.181
_refine_ls_abs_structure_details
;
 Flack x determined using 990 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.210
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2964
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.210
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0438
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0804P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1177
_refine_ls_wR_factor_ref         0.1412
_reflns_Friedel_coverage         0.693
_reflns_Friedel_fraction_full    0.959
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                2709
_reflns_number_total             2964
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03127h2.cif
_cod_data_source_block           sjg-rp-03-191-p_mo
_cod_original_cell_volume        1713.92(16)
_cod_database_code               7123489
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.960
_reflns_odcompleteness_completeness 92.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.09
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C18(H18), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C15(H15A,H15B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C7(H7), C4(H4), C6(H6), C11(H11), C14(H14), C3(H3), C12(H12),
 C13(H13)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C1(H1A,H1B,H1C)
;
_shelx_res_checksum              96505
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.212
_oxdiff_exptl_absorpt_empirical_full_min 0.859