A green and cascade synthesis of functionalized 2-aminothiophenes from ketene dithioacetals.
Chahal, Mohit; Shaw, Ranjay; Yadav, Pratik; Bhardwaj, Vishnu; Althagafi, Ismail; Pratap, Ramendra; Organic & biomolecular chemistry 23 (2025) 10106–10117; doi:10.1039/d5ob01121c

data_7160800
_publ_section_title
;
 A green and cascade synthesis of functionalized 2-aminothiophenes from
 ketene dithioacetals.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10106
_journal_page_last               10117
_journal_paper_doi               10.1039/d5ob01121c
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         '0.25(C11 H13 N3 O2 S)'
_chemical_formula_sum            'C2.75 H3.25 N0.75 O0.5 S0.25'
_chemical_formula_weight         62.828
_chemical_name_systematic
'methyl 3-amino-4-cyano-5-(pyrrolidin-1-yl)thiophene-2-carboxylate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-27
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-08-27 deposited with the CCDC.	2025-09-29 downloaded from the CCDC.
;
_cell_angle_alpha                105.928(5)
_cell_angle_beta                 93.244(5)
_cell_angle_gamma                111.848(6)
_cell_formula_units_Z            8
_cell_length_a                   7.9380(5)
_cell_length_b                   8.4101(4)
_cell_length_c                   10.0296(6)
_cell_measurement_reflns_used    2716
_cell_measurement_temperature    298
_cell_measurement_theta_max      29.3130
_cell_measurement_theta_min      2.1360
_cell_volume                     588.09(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 0.7782
_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    -23.00  39.00   0.50    6.00    --    6.31 -99.00  90.00  124
  2  \w     -4.00  69.00   0.50    6.00    --    6.31  38.00-180.00  146
  3  \w    -13.00  36.00   0.50    6.00    --    6.31 -99.00  60.00   98
  4  \w    -39.00  18.00   0.50    6.00    --    6.31 -38.00 -30.00  114
  5  \w     -1.00  76.00   0.50    6.00    --    6.31  77.00-120.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0442154000
_diffrn_orient_matrix_UB_12      -0.0955203000
_diffrn_orient_matrix_UB_13      -0.0193064000
_diffrn_orient_matrix_UB_21      0.0148410000
_diffrn_orient_matrix_UB_22      -0.0072289000
_diffrn_orient_matrix_UB_23      -0.0700983000
_diffrn_orient_matrix_UB_31      0.0859951000
_diffrn_orient_matrix_UB_32      -0.0038260000
_diffrn_orient_matrix_UB_33      0.0172904000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 0.7782
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6805
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 0.7782
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         31.06
_diffrn_reflns_theta_min         2.15
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.269
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87939
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear grayish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   grayish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_description       irregular
_exptl_crystal_F_000             264.411
_exptl_crystal_preparation       'best crytal was selected under microscope'
_exptl_crystal_recrystallization_method
'Slow evaporation in Ethyl acetate and hexane'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.4153
_refine_diff_density_min         -0.3448
_refine_diff_density_rms         0.0698
_refine_ls_d_res_high            0.6888
_refine_ls_d_res_low             9.4908
_refine_ls_goodness_of_fit_ref   1.0626
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    19
_refine_ls_number_parameters     156
_refine_ls_number_reflns         2944
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0626
_refine_ls_R_factor_all          0.0745
_refine_ls_R_factor_gt           0.0519
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0727P)^2^+0.0793P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1386
_refine_ls_wR_factor_ref         0.1521
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              11
_reflns_limit_k_min              -12
_reflns_limit_l_max              14
_reflns_limit_l_min              0
_reflns_number_gt                2024
_reflns_number_total             2944
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ob01121c3.cif
_cod_data_source_block           5B_auto
_cod_depositor_comments
'Adding full bibliography for 7160799--7160802.cif.'
_cod_database_code               7160800
_chemical_oxdiff_formula         'C H N S O'
_chemical_oxdiff_usercomment     26-08-2025
_cell_oxdiff_angle_alpha         105.929(5)
_cell_oxdiff_angle_beta          93.244(5)
_cell_oxdiff_angle_gamma         111.848(6)
_cell_oxdiff_length_a            7.9380(5)
_cell_oxdiff_length_b            8.4101(4)
_cell_oxdiff_length_c            10.0296(6)
_cell_oxdiff_measurement_reflns_used 2716
_cell_oxdiff_volume              588.09(6)
_diffrn_oxdiff_digest_hkl
;
01f352a854e344e6162aa1fb207766031f9012
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Rotating group:
 N005(H00a,H00b)
2.b Secondary CH2 refined with riding coordinates:
 C009(H00c,H00d), C00E(H00e,H00f), C00F(H00g,H00h), C00G(H00i,H00j)
2.c Idealised Me refined as rotating group:
 C00H(H00k,H00l,H00m)
;
_olex2_exptl_crystal_mounting_method NA
_olex2_submission_original_sample_id 5b
_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 1.235
_oxdiff_exptl_absorpt_empirical_full_min 0.680