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_7123490
_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         '4(C18 H21 N O2 S)'
_chemical_formula_sum            'C72 H84 N4 O8 S4'
_chemical_formula_weight         1261.67
_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     dual
_audit_creation_date             2018-10-24
_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                 107.315(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.8848(4)
_cell_length_b                   7.37022(15)
_cell_length_c                   25.6676(6)
_cell_measurement_reflns_used    10463
_cell_measurement_temperature    150
_cell_measurement_theta_max      72.2580
_cell_measurement_theta_min      2.5710
_cell_volume                     3230.05(13)
_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   -191.00 -42.00   1.00    8.00    -- -101.00   0.00-108.00  149
  2  \w   -122.00   2.00   1.00    8.00    --  -32.00 -72.00 108.00  124
  3  \w   -191.00 -77.00   1.00    8.00    -- -101.00 -72.00  36.00  114
  4  \w   -135.00 -68.00   1.00    8.00    -- -101.00  72.00-180.00   67
  5  \w    -64.00  33.00   1.00    8.00    --  -32.00   0.00-108.00   97
  6  \w    -44.00 -14.00   1.00    8.00    -- -101.00  72.00 -36.00   30
  7  \w    -53.00 -23.00   1.00    8.00    -- -101.00  72.00 108.00   30
  8  \w   -191.00-161.00   1.00    8.00    -- -101.00 -72.00-180.00   30
  9  \w    -80.00 -18.00   1.00    8.00    -- -101.00  72.00-108.00   62
 10  \w   -135.00 -18.00   1.00    8.00    -- -101.00  72.00  36.00  117
 11  \w   -191.00 -67.00   1.00    8.00    -- -101.00 -72.00 -36.00  124
 12  \w   -169.00 -67.00   1.00    8.00    -- -101.00 -72.00-108.00  102
 13  \w    -98.00  40.00   1.00    8.00    --  -32.00   0.00-180.00  138
 14  \w   -138.00 -74.00   1.00    8.00    -- -101.00   0.00 108.00   64
 15  \w    -66.00  58.00   1.00    8.00    --  -32.00  72.00-180.00  124
 16  \w   -191.00 -67.00   1.00    8.00    -- -101.00 -72.00 108.00  124
 17  \w   -147.00-116.00   1.00    8.00    -- -101.00   0.00 -36.00   31
 18  \w    -30.00   0.00   1.00    8.00    --  -32.00 -72.00  36.00   30
 19  \w   -191.00 -42.00   1.00    8.00    -- -101.00   0.00  36.00  149
 20  \w    -66.00 -33.00   1.00    8.00    --  -32.00  72.00-108.00   33
;
_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      0.0831101000
_diffrn_orient_matrix_UB_12      -0.0689287000
_diffrn_orient_matrix_UB_13      0.0048343000
_diffrn_orient_matrix_UB_21      -0.0075069000
_diffrn_orient_matrix_UB_22      0.0737314000
_diffrn_orient_matrix_UB_23      -0.0574856000
_diffrn_orient_matrix_UB_31      0.0343415000
_diffrn_orient_matrix_UB_32      0.1831158000
_diffrn_orient_matrix_UB_33      0.0249358000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0975
_diffrn_reflns_av_unetI/netI     0.0798
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            35767
_diffrn_reflns_point_group_measured_fraction_full 0.919
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        64.995
_diffrn_reflns_theta_max         64.995
_diffrn_reflns_theta_min         1.803
_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    1.829
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39927
_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    1.297
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.278
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.099
_refine_ls_abs_structure_details
;
 Flack x determined using 2400 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.028(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     789
_refine_ls_number_reflns         10110
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.1003
_refine_ls_R_factor_gt           0.0818
_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^)+(0.1496P)^2^+1.7551P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2130
_refine_ls_wR_factor_ref         0.2400
_reflns_Friedel_coverage         0.691
_reflns_Friedel_fraction_full    0.822
_reflns_Friedel_fraction_max     0.822
_reflns_number_gt                8044
_reflns_number_total             10110
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03127h2.cif
_cod_data_source_block           sjg-rp-02-163_cu
_cod_original_cell_volume        3230.06(13)
_cod_database_code               7123490
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.711
_shelx_estimated_absorpt_t_min   0.711
_reflns_odcompleteness_completeness 98.09
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.79
_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. Restrained distances
 C9-C8
 1.7 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.001
Uanis(C8) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
4.a Ternary CH refined with riding coordinates:
 C44(H44), C65(H65), C47(H47), C62(H62), C29(H29), C25(H25), C9(H9), C12(H12)
4.b Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C64(H64A,H64B), C45(H45A,H45B), C63(H63A,H63B), C27(H27A,
 H27B), C28(H28A,H28B), C10(H10A,H10B), C11(H11A,H11B)
4.c Aromatic/amide H refined with riding coordinates:
 C59(H59), C41(H41), C53(H53), C3(H3), C71(H71), C69(H69), C67(H67),
 C012(H012), C21(H21), C56(H56), C42(H42), C68(H68), C51(H51), C52(H52),
 C38(H38), C32(H32), C6(H6), C50(H50), C39(H39), C49(H49), C31(H31), C60(H60),
 C70(H70), C4(H4), C35(H35), C7(H7), C22(H22), C33(H33), C57(H57), C34(H34),
 C24(H24), C15(H15), C16(H16), C17(H17), C18(H18), C14(H14)
4.d Fitted hexagon refined as free rotating group:
 C15(C16,C17,C18,C13,C14)
4.e Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C43(H43A,H43B,H43C), C36(H36A,H36B,H36C), C54(H54A,H54B,
 H54C), C19(H19A,H19B,H19C), C26(H26A,H26B,H26C), C1(H1A,H1B,H1C), C8(H8A,H8B,
 H8C)
;
_shelx_res_checksum              90817
_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 2.012
_oxdiff_exptl_absorpt_empirical_full_min 0.617