Enantioselective Inverse-Electron Demand Aza-Diels–Alder Reaction: ipso,α-Selectivity of Silyl Dienol Ethers
Laina-Martín, Víctor; Humbrías-Martín, Jorge; Mas-Ballesté, Rubén; Fernández-Salas, Jose A.; Alemán, José; ACS Catalysis 11 (2021) 12133–12145; doi:10.1021/acscatal.1c03390

data_4519070
_publ_section_title
;
 Enantioselective Inverse-Electron Demand Aza-Diels--Alder Reaction:
 ipso,\a-Selectivity of Silyl Dienol Ethers
;
_journal_issue                   19
_journal_name_full               'ACS Catalysis'
_journal_page_first              12133
_journal_page_last               12145
_journal_paper_doi               10.1021/acscatal.1c03390
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_sum            'C31 H31 N O6.5 S'
_chemical_formula_weight         553.63
_chemical_name_common            VL_909_aftercol_250K
_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
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.5571(2)
_cell_length_b                   12.9667(4)
_cell_length_c                   21.3679(6)
_cell_measurement_reflns_used    8114
_cell_measurement_temperature    250.(2)
_cell_measurement_theta_max      21.7759
_cell_measurement_theta_min      2.4701
_cell_volume                     2925.07(13)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      250.(2)
_diffrn_detector_area_resol_mean 8.3333
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker Kappa Apex II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            36993
_diffrn_reflns_theta_full        25.34
_diffrn_reflns_theta_max         25.34
_diffrn_reflns_theta_min         3.13
_exptl_absorpt_coefficient_mu    0.156
_exptl_absorpt_correction_T_max  0.99
_exptl_absorpt_correction_T_min  0.88
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1168
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.094
_refine_diff_density_max         0.619
_refine_diff_density_min         -0.250
_refine_ls_abs_structure_details
;

Flack x determined using 1900 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     372
_refine_ls_number_reflns         5339
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0567
_refine_ls_R_factor_gt           0.0483
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0997P)^2^+0.9066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1353
_refine_ls_wR_factor_ref         0.1444
_reflns_number_gt                4722
_reflns_number_total             5339
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c03390_si_002.cif
_cod_data_source_block           03024DanielGonzalez
_cod_original_formula_sum        'C31 H31 N O6.50 S'
_cod_database_code               4519070
_shelx_res_checksum              60681
_shelx_hkl_checksum              89276