cis-Dihydroxylated α-Trifluoromethylated N,O-Acetal from l-Tartaric Acid: Synthesis of Tetrasubstituted Stereocenter via Diastereoselective Pictet-Spengler Cyclization of N-Acyliminium Ions
Ben Jamaa, Abdelkhalek; Latrache, Mohammed; Riguet, Emmanuel; Grellepois, Fabienne; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.0c00801

data_4038613
_publ_section_title
;
 cis-Dihydroxylated \a-Trifluoromethylated N,O-Acetal from l-Tartaric
 Acid: Synthesis of Tetrasubstituted Stereocenter via Diastereoselective
 Pictet-Spengler Cyclization of N-Acyliminium Ions
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00801
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H14 Cl2 F3 N O3'
_chemical_formula_sum            'C16 H14 Cl2 F3 N O3'
_chemical_formula_weight         396.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.5277(9)
_cell_length_b                   16.5073(15)
_cell_length_c                   19.0274(16)
_cell_measurement_reflns_used    9832
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      72.276
_cell_measurement_theta_min      3.54
_cell_volume                     3306.7(5)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.02
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0551
_diffrn_reflns_av_unetI/netI     0.0355
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            40163
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.269
_diffrn_reflns_theta_min         3.545
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.994
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5346
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1176 before and 0.0857 after correction. The Ratio of minimum to maximum transmission is 0.7094. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_lustre     clear
_exptl_crystal_density_diffrn    1.592
_exptl_crystal_description       prism
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.452
_exptl_crystal_size_mid          0.336
_exptl_crystal_size_min          0.136
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.216
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 2519 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.099(5)
_refine_ls_extinction_coef       0.00017(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     456
_refine_ls_number_reflns         6490
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0350
_refine_ls_R_factor_gt           0.0317
_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^)+(0.0187P)^2^+2.1301P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0682
_refine_ls_wR_factor_ref         0.0702
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                6086
_reflns_number_total             6490
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00801_si_002.cif
_cod_data_source_block           cu_19fg045_0m
_cod_database_code               4038613
_shelx_shelxl_version_number     2017/1
_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:
 C00X(H00X), C013(H013), C4(H4), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C014(H01A,H01B), C019(H01C,H01D), C15(H15A,H15B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C00J(H00J), C00L(H00L), C10(H10), C12(H12)
2.d Idealised Me refined as rotating group:
 C01D(H01E,H01F,H01G), C01E(H01H,H01I,H01J), C1(H1A,H1B,H1C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              12779
_shelx_hkl_checksum              76717
_olex2_submission_special_instructions 'No special instructions were received'