HFIP-mediated cascade aminomethylation and intramolecular cyclization of allenamides with <i>N</i>,<i>O</i>-acetals to access tetrahydro-β-carboline derivatives.
Chaudhary, Dhananjay; Maurya, Chandra Shekhar; Unnikrishnan, Urmila; Kuram, Malleswara Rao; Chemical communications (Cambridge, England) 61 (2025) 2981–2984; doi:10.1039/d5cc00154d

data_7134189
_publ_section_title
;
 HFIP-mediated cascade aminomethylation and intramolecular cyclization of
 allenamides with <i>N</i>,<i>O</i>-acetals to access
 tetrahydro-&#x3b2;-carboline derivatives.
;
_journal_issue                   14
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2981
_journal_page_last               2984
_journal_paper_doi               10.1039/d5cc00154d
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C26 H31 N3 O3 S'
_chemical_formula_sum            'C26 H31 N3 O3 S'
_chemical_formula_weight         465.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2024-10-14 deposited with the CCDC.	2025-01-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.373(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6627(2)
_cell_length_b                   15.3055(2)
_cell_length_c                   12.8279(2)
_cell_measurement_reflns_used    10343
_cell_measurement_temperature    291.86(10)
_cell_measurement_theta_max      77.8100
_cell_measurement_theta_min      3.5600
_cell_volume                     2437.34(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.86(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.951
_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    -75.00  21.00   0.50    0.07    --  -47.50  89.00-131.00  192
  2  \w     28.00  53.00   0.50    0.07    --   47.50 -89.00 113.00   50
  3  \w   -155.00 -88.00   0.50    0.27    --  -91.75 -89.00 113.00  134
  4  \w    -79.00 -54.00   0.50    0.27    --  -91.75  89.00-131.00   50
  5  \w     37.00 105.00   0.50    0.27    --  109.69 -89.00 113.00  136
  6  \w    125.00 154.00   0.50    0.27    --  109.69  89.00-131.00   58
  7  \w    -23.00  19.00   0.50    0.07    --  -47.50  19.00 -60.00   84
  8  \w   -112.00 -32.00   0.50    0.07    --  -47.50 -57.00 120.00  160
  9  \w    -17.00   9.00   0.50    0.07    --  -47.50  19.00-120.00   52
 10  \w    -80.00 -32.00   0.50    0.27    --  -91.75 125.00 -30.00   96
 11  \w   -108.00 -82.00   0.50    0.27    --  -91.75 -38.00 150.00   52
 12  \w    -52.00 -19.00   0.50    0.27    --  -91.75  57.00  60.00   66
 13  \w   -162.00-127.00   0.50    0.27    --  -91.75 -38.00 150.00   70
 14  \w     37.00  62.00   0.50    0.27    --  109.69 -57.00-120.00   50
 15  \w     37.00  62.00   0.50    0.27    --  109.69 -57.00 -30.00   50
 16  \w     40.00  73.00   0.50    0.27    --  109.69-125.00 -90.00   66
 17  \w     78.00 103.00   0.50    0.27    --  109.69-125.00 -90.00   50
 18  \w     37.00  65.00   0.50    0.27    --  109.69 -57.00 -90.00   56
 19  \w     38.00  64.00   0.50    0.27    --  109.69 -57.00 -60.00   52
 20  \w     47.00 108.00   0.50    0.27    --  109.69-125.00  90.00  122
 21  \w     39.00  64.00   0.50    0.27    --  109.69 -57.00-180.00   50
 22  \w     43.00  68.00   0.50    0.27    --  109.69 -57.00  30.00   50
 23  \w     95.00 121.00   0.50    0.27    --  109.69  57.00 -60.00   52
 24  \w    144.00 176.00   0.50    0.27    --  109.69  57.00 -60.00   64
 25  \w     38.00  64.00   0.50    0.27    --  109.69 -57.00 150.00   52
 26  \w     38.00 104.00   0.50    0.27    --  109.69 -77.00 -90.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0374896000
_diffrn_orient_matrix_UB_12      -0.0901088000
_diffrn_orient_matrix_UB_13      -0.0466701000
_diffrn_orient_matrix_UB_21      0.0619240000
_diffrn_orient_matrix_UB_22      0.0146694000
_diffrn_orient_matrix_UB_23      -0.0905955000
_diffrn_orient_matrix_UB_31      0.1007146000
_diffrn_orient_matrix_UB_32      -0.0424244000
_diffrn_orient_matrix_UB_33      0.0680471000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            17447
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.005
_diffrn_reflns_theta_min         3.560
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.437
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61223
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.88a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.269
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.0036(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     313
_refine_ls_number_reflns         4961
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0500
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0707P)^2^+0.2638P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1232
_refine_ls_wR_factor_ref         0.1302
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4136
_reflns_number_total             4961
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00154d2.cif
_cod_data_source_block           xrf27062024c_auto
_cod_depositor_comments          'Adding full bibliography for 7134189.cif.'
_cod_original_cell_volume        2437.34(6)
_cod_database_code               7134189
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C26 H31 N3 O3 S'
_reflns_odcompleteness_completeness 99.89
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C21(H21A,H21B), C25(H25A,H25B), C22(H22A,
 H22B), C24(H24A,H24B), C23(H23A,H23B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C1(H1), C4(H4), C6(H6), C11(H11), C10(H10), C9(H9)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              1924
_shelx_hkl_checksum              1272
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.538
_oxdiff_exptl_absorpt_empirical_full_min 0.595