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_4037871
_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         'C29 H26 Br F3 N2 O3'
_chemical_formula_sum            'C29 H26 Br F3 N2 O3'
_chemical_formula_weight         587.42
_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             2019-09-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6343(5)
_cell_length_b                   11.7382(5)
_cell_length_c                   20.6645(10)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      27.976
_cell_measurement_theta_min      2.584
_cell_volume                     2579.5(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_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0841
_diffrn_reflns_av_unetI/netI     0.0541
_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       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            34484
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.994
_diffrn_reflns_theta_min         2.766
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.650
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5520
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.513
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.029
_exptl_crystal_size_mid          0.026
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.262
_refine_diff_density_min         -0.305
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 1853 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.022(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         5062
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0292
_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^)+0.6503P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0688
_reflns_Friedel_coverage         0.766
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4557
_reflns_number_total             5062
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03076_si_003.cif
_cod_data_source_block           6
_cod_database_code               4037871
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.954
_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 O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C26(H26A,H26B), C16(H16A,H16B), C28(H28A,H28B), C29(H29A,H29B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C24(H24), C14(H14), C23(H23), C12(H12), C15(H15), C5(H5), C11(H11),
 C22(H22), C6(H6), C7(H7), C3(H3A), C20(H20), C4(H4), C21(H21)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_shelx_res_checksum              49864
_shelx_hkl_checksum              18267
_olex2_submission_special_instructions 'No special instructions were received'