Asymmetric N-aminoalkylation of 3-substituted indoles by N-protected N,O-acetals: an access to chiral propargyl aminals.
Yang, Junxian; He, Zeyuan; Hong, Liang; Sun, Wangsheng; Wang, Rui; Organic & biomolecular chemistry 18 (2020) 4169–4173; doi:10.1039/d0ob00795a

data_7157502
_publ_section_title
;
 Asymmetric N-aminoalkylation of 3-substituted indoles by N-protected
 N,O-acetals: an access to chiral propargyl aminals.
;
_journal_issue                   22
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4169
_journal_page_last               4173
_journal_paper_doi               10.1039/d0ob00795a
_journal_volume                  18
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H24 N2 O2 S'
_chemical_formula_sum            'C26 H24 N2 O2 S'
_chemical_formula_weight         428.53
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-27 deposited with the CCDC.	2020-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.3559(2)
_cell_length_b                   9.3559(2)
_cell_length_c                   60.611(3)
_cell_measurement_reflns_used    8250
_cell_measurement_temperature    292.01(10)
_cell_measurement_theta_max      64.6380
_cell_measurement_theta_min      4.7640
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_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      292.01(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_details
;
  1 omega  -87.00  -52.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  178.0000  -30.0000 35

  2 omega  -76.00  -38.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  -63.0000 -150.0000 38

  3 omega  -84.00  -58.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  178.0000 -180.0000 26

  4 omega  -19.00   16.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  -63.0000 -150.0000 35

  5 omega   77.00  122.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  154.0000 -145.0000 45

  6 omega   52.00  122.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000  -30.0000 70

  7 omega   49.00   79.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000 -180.0000 30

  8 omega   20.00   46.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   81.0000  -71.8715 26

  9 omega   21.00   47.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   79.0000  -28.0199 26

 10 omega   85.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   50.0000  120.0000 93

 11 omega   34.00   92.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000 -150.0000 58

 12 omega   82.00  108.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   69.0000 -105.0520 26

 13 omega   87.00  128.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 41

 14 omega  131.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 47

 15 omega   37.00   92.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -38.0000   90.0000 55

 16 omega   38.00  148.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000    0.0000   90.0000 110

 17 omega   53.00  128.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -63.0000 -150.0000 75

 18 omega   35.00   60.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -25.0000   60.0000 25

 19 omega  130.00  168.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  120.0000 38

 20 omega  -79.00   14.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  -51.0000   40.0000 93

 21 omega  -79.00   23.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  -77.0000  -90.0000 102

 22 omega   31.00  125.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   51.0000 -172.0000 94

 23 omega   32.00  123.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000   57.0000   90.0000 91

 24 omega  -17.00   86.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       54.0000  -77.0000 -150.0000 103

 25 omega   84.00  175.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000 -180.0000 91

 26 omega   35.00  115.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -120.0000 80

 27 omega   76.00  157.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 81

 28 omega   68.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   25.0000  -30.0000 110

 29 omega  100.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -120.0000 78
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0233486000
_diffrn_orient_matrix_UB_12      0.0410345000
_diffrn_orient_matrix_UB_13      -0.0243483000
_diffrn_orient_matrix_UB_21      -0.1282919000
_diffrn_orient_matrix_UB_22      -0.0937255000
_diffrn_orient_matrix_UB_23      -0.0066887000
_diffrn_orient_matrix_UB_31      -0.1005353000
_diffrn_orient_matrix_UB_32      0.1290276000
_diffrn_orient_matrix_UB_33      0.0028905000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0301
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       73
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_diffrn_reflns_theta_max         70.919
_diffrn_reflns_theta_min         4.783
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.248
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21466
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.073
_exptl_crystal_description       block
_exptl_crystal_F_000             1808
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.438
_refine_diff_density_min         -0.310
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 1294 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.079(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.868
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         4996
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      0.891
_refine_ls_R_factor_all          0.0950
_refine_ls_R_factor_gt           0.0870
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1797P)^2^+3.8300P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2483
_refine_ls_wR_factor_ref         0.2589
_reflns_Friedel_coverage         0.633
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.969
_reflns_number_gt                4236
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_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob00795a2.cif
_cod_data_source_block           yangjx_0109
_cod_depositor_comments          'Adding full bibliography for 7157502.cif.'
_cod_original_cell_volume        5305.5(4)
_cod_database_code               7157502
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12)
\\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C19')
\\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(S1') \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: H20(0.5) H20A(0.3) H21(0.7) H21A(0.5) S1(0.5) C19(0.7) H19(0.7)
 S1'(0.5) C19'(0.3) H19'(0.3)
4.a Ternary CH refined with riding coordinates:
 C15(H15)
4.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C0AA(H0AA), C4(H4), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C20(H20), C20(H20A), C21(H21), C21(H21A),
 C19(H19), C19'(H19')
4.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              54171
_shelx_fab_checksum              88943
_olex2_date_sample_data_collection 2019-01-10
_olex2_submission_special_instructions 'No special instructions were received'