Organocatalytic Asymmetric Hetero-Diels-Alder Reaction of in-situ Generated Dienes: Access to α,β-Unsaturated δ-Lactones Featuring CF3-Substituted Quaternary Stereocenter.
Joshi, Harshit; Yadav, Ankit; Das, Arko; Singh, Vinod K.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b03076

data_4037870
_publ_section_title
;
 Organocatalytic Asymmetric Hetero-Diels-Alder Reaction of in-situ
 Generated Dienes: Access to \a,\b-Unsaturated \d-Lactones Featuring
 CF3-Substituted Quaternary Stereocenter.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03076
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C25 H17 Br F3 N O3'
_chemical_formula_sum            'C25 H17 Br F3 N O3'
_chemical_formula_weight         516.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.998(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8347(5)
_cell_length_b                   22.0058(12)
_cell_length_c                   10.1652(6)
_cell_measurement_reflns_used    9965
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      28.259
_cell_measurement_theta_min      2.214
_cell_volume                     2191.6(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.998
_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  0.0466
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            33659
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.278
_diffrn_reflns_theta_min         2.734
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.929
_exptl_absorpt_correction_T_max  28.26
_exptl_absorpt_correction_T_min  2.21
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1122 before and 0.0829 after correction. The Ratio of minimum to maximum transmission is 0.8666. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.565
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_size_max          0.052
_exptl_crystal_size_mid          0.023
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.865
_refine_diff_density_min         -0.583
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 4376 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.034(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     595
_refine_ls_number_reflns         10757
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0293
_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^)+(0.0086P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0685
_refine_ls_wR_factor_ref         0.0701
_reflns_Friedel_coverage         0.934
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                9967
_reflns_number_total             10757
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03076_si_002.cif
_cod_data_source_block           4ac
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4037870
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.906
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C16(H16A,H16B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C23(H23), C24(H24), C47(H47), C39(H39), C12(H12), C48(H48),
 C4(H4), C45(H45), C37(H37), C15(H15), C11(H11), C49(H49), C36(H36), C46(H46),
 C27(H27), C3(H3), C7(H7), C14(H14), C21(H21), C20(H20), C22(H22), C31(H31),
 C40(H40), C5(H5), C29(H29), C6(H6), C28(H28), C30(H30)
;
_shelx_res_checksum              28445
_shelx_hkl_checksum              15664
_olex2_submission_special_instructions 'No special instructions were received'