Catalytic Asymmetric [4+2]-Cycloaddition of Dienes with Aldehydes
Liu, Luping; Kim, Hyejin; Xie, Youwei; Farès, Christophe; Kaib, Philip S. J.; Goddard, Richard; List, Benjamin; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b08357

data_4126474
_publ_section_title
;
 Catalytic Asymmetric [4+2]-Cycloaddition of Dienes with Aldehydes
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b08357
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety
'C65.60 H33 F44.80 N3 O7.20 P2 S10, 0.15(Cl6 Cl4), C5.20, C4.40'
_chemical_formula_sum            'C83.2 H33 Cl3.8 F44.8 N3 O7.2 P2 S10'
_chemical_formula_weight         2558.17
_chemical_name_systematic
;
 N,N'-((11bS,11b'S)-azanediylbis(2,6-bis(3,5-bis(pentafluoro-
 1^6^-sulfanyl)phenyl)-41^5^-dinaphtho[2,1-d:1',2'-
 f][1,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1,1,1-
 trifluoromethanesulfonamide)
 dichloromethane hexane solute
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_block_code                KIH-KA-684_100K_10698_4c
_audit_creation_date             2017-04-26
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.7656(13)
_cell_length_b                   41.726(3)
_cell_length_c                   14.4668(10)
_cell_measurement_reflns_used    9826
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      57.3633
_cell_measurement_theta_min      5.0011
_cell_volume                     11327.7(14)
_computing_cell_refinement       'SAINT software (Bruker AXS, 2004)'
_computing_data_collection       'APEX2 (Bruker AXS, 2005-2013)'
_computing_data_reduction        'SAINT software (Bruker AXS, 2004)'
_computing_molecular_graphics    'DIAMOND (Crystal Impact GbR, 1997-2014)'
_computing_structure_refinement  'SHELXL (G. M. Sheldrick, 2013)'
_computing_structure_solution    'SHELXS (G. M. Sheldrick, 2013)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 66.67
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker AXS X8 Proteum'
_diffrn_measurement_method       'CCD \f- and \w-scans'
_diffrn_radiation_monochromator  'MONTEL graded multilayer optic'
_diffrn_radiation_source         '0.2 x 2mm^2^ focus rotating anode'
_diffrn_radiation_type           Cu-K\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0717
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            165258
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        63.596
_diffrn_reflns_theta_max         63.596
_diffrn_reflns_theta_min         4.831
_diffrn_source                   'Bruker AXS FR591 rotating anode'
_exptl_absorpt_coefficient_mu    4.015
_exptl_absorpt_correction_T_max  0.90830
_exptl_absorpt_correction_T_min  0.51138
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   'SADABS (Bruker AXS, 2012)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_description       plate
_exptl_crystal_F_000             5074
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent:  dichloromethane,hexane'
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.189
_exptl_crystal_size_min          0.030
_refine_diff_density_max         0.905
_refine_diff_density_min         -0.805
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details
;
 Flack x determined using 6454 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.513
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1405
_refine_ls_number_reflns         18356
_refine_ls_number_restraints     46
_refine_ls_restrained_S_all      1.522
_refine_ls_R_factor_all          0.0785
_refine_ls_R_factor_gt           0.0674
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1847
_refine_ls_wR_factor_ref         0.1920
_reflns_Friedel_coverage         0.822
_reflns_Friedel_fraction_full    0.980
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                16034
_reflns_number_total             18356
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b08357_si_002.cif
_cod_data_source_block           4c
_cod_original_cell_volume        11327.8(14)
_cod_original_formula_sum        'C83.20 H33 Cl3.80 F44.80 N3 O7.20 P2 S10'
_cod_database_code               4126474
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.379
_shelx_estimated_absorpt_t_max   0.889
_shelx_res_checksum              60555
_shelx_hkl_checksum              66233