Enamine-mediated Mannich reaction of cyclic N,O-acetals and amido acetals: the multigram synthesis of pyrrolidine alkaloid precursors
Turmanov, Rakhymzhan A.; Smolobochkin, Andrey V.; Gazizov, Almir S.; Rizbayeva, Tanzilya S.; Zapylkin, Danil D.; Voronina, Julia K.; Voloshina, Alexandra D.; Syakaev, Victor V.; Kurenkov, Alexey V.; Burilov, Alexander R.; Pudovik, Michail A.; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01276F

data_7158856
_publ_section_title
;
 Enamine-mediated Mannich reaction of cyclic N,O-acetals and amido
 acetals: the multigram synthesis of pyrrolidine alkaloid precursors
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01276F
_journal_year                    2022
_chemical_formula_moiety         'C19 H21 N O3 S'
_chemical_formula_sum            'C19 H21 N O3 S'
_chemical_formula_weight         343.43
_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   geom
_audit_creation_date             2022-05-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-05-26 deposited with the CCDC.	2022-08-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.1800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   37.3753(9)
_cell_length_b                   7.6042(3)
_cell_length_c                   11.9845(5)
_cell_measurement_reflns_used    8698
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      30.41
_cell_measurement_theta_min      2.18
_cell_volume                     3400.9(2)
_computing_cell_refinement       'SAINT V8.35A (?, 2016)'
_computing_data_reduction        'SAINT V8.35A (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0483
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       50
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            37024
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.999
_diffrn_reflns_theta_min         1.637
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.207
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6895
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0608 before and 0.0527 after correction.
The Ratio of minimum to maximum transmission is 0.9241.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       prizm
_exptl_crystal_F_000             1456
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.457
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     454
_refine_ls_number_reflns         9057
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0621
_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^)+(0.0434P)^2^+2.9916P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1357
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7155
_reflns_number_total             9057
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01276f2.cif
_cod_data_source_block           a_a_CCDC4
_cod_database_code               7158856
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.974
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H2BA)=Sof(H5BC)=Sof(H5BD)=Sof(C3B')=Sof(H3BC)=Sof(H3BD)=Sof(C4B')=
 Sof(H4BC)=Sof(H4BD)=1-FVAR(1)
 Sof(H2B)=Sof(H5BA)=Sof(H5BB)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4BA)=
 Sof(H4BB)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C2B(H2B), C2B(H2BA), C2A(H2A)
3.b Secondary CH2 refined with riding coordinates:
 C5B(H5BA,H5BB), C5B(H5BC,H5BD), C13B(H13A,H13B), C3B(H3BA,H3BB), C4B(H4BA,
 H4BB), C3B'(H3BC,H3BD), C4B'(H4BC,H4BD), C3A(H3AA,H3AB), C4A(H4AA,H4AB),
 C5A(H5AA,H5AB), C13A(H13C,H13D)
3.c Aromatic/amide H refined with riding coordinates:
 C7B(H7B), C8B(H8B), C10B(H10B), C11B(H11B), C16B(H16B), C17B(H17B),
 C18B(H18B), C19B(H19B), C20B(H20B), C7A(H7A), C8A(H8A), C10A(H10A), C11A(H11A),
  C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A)
3.d Idealised Me refined as rotating group:
 C12B(H12A,H12B,H12C), C12A(H12D,H12E,H12F)
;
_shelx_res_checksum              27044
_shelx_hkl_checksum              97237
_olex2_submission_special_instructions 'No special instructions were received'