Synthesis of Aza-Quaternary Centers via Pictet–Spengler Reactions of Ketonitrones
Lynch-Colameta, Tessa; Greta, Sarah; Snyder, Scott A.; Chemical Science  (2021) –; doi:10.1039/D1SC00882J

data_1561050
_publ_section_title
;
 Synthesis of Aza-Quaternary Centers via Pictet--Spengler Reactions of
 Ketonitrones
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC00882J
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H21 Br N2 O2'
_chemical_formula_sum            'C25 H21 Br N2 O2'
_chemical_formula_weight         461.35
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-12-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6219)
;
_audit_update_record
;
2021-02-02 deposited with the CCDC.	2021-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8948(6)
_cell_length_b                   10.3781(6)
_cell_length_c                   20.5618(13)
_cell_measurement_reflns_used    9573
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.07
_cell_measurement_theta_min      2.20
_cell_volume                     2111.5(2)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_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    'XT 2014/5 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON 100'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            CMOS
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            43364
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.723
_diffrn_reflns_theta_min         2.198
_diffrn_source                   'micro-focus X-ray tube'
_diffrn_source_type              'INCOATEC ImuS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.971
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6638
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. 
wR2(int) was 0.0841 before and 0.0740 after correction. 
The Ratio of minimum to maximum transmission is 0.8901.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.451
_exptl_crystal_description       needle
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.051
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.727
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1781 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         5432
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0338
_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^)+(0.0310P)^2^+0.0802P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0616
_refine_ls_wR_factor_ref         0.0646
_reflns_Friedel_coverage         0.762
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                4699
_reflns_number_total             5432
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00882j2.cif
_cod_data_source_block           0953_tlc_snyder_2
_cod_database_code               1561050
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.798
_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.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13), C14(H14),
 C21(H21), C22(H22), C23(H23), C24(H24), C25(H25)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C)
;
_shelx_res_checksum              6387
_shelx_hkl_checksum              1626
_olex2_submission_special_instructions 'No special instructions were received'