Trienamine-mediated asymmetric [4+2]-cycloaddition of alpha,beta-unsaturated ester surrogates applying 4-nitro-5-styrylisoxazoles
Yang Li; Francisco Javier Lopez-Delgado; Danny Kaare Bech Jorgensen; Rune Pagh Nielsen; Hao Jiang; Karl Anker Jorgensen; Chem.Commun. 50 (2014) 15689–; doi:10.1039/C4cc08171D

data_7116104
_publ_section_title
;
 Trienamine-mediated asymmetric [4+2]-cycloaddition of
 alpha,beta-unsaturated ester surrogates applying
 4-nitro-5-styrylisoxazoles
;
_journal_name_full               Chem.Commun.
_journal_page_first              15689
_journal_paper_doi               10.1039/C4cc08171D
_journal_volume                  50
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H27 Br N2 O5'
_chemical_formula_sum            'C27 H27 Br N2 O5'
_chemical_formula_weight         539.41
_chemical_name_systematic
'2-(5-hydroxy-4-methyl-2-(4-methyl-3-nitropyrrolidin-2-yl)-1,2,3,6-tetrahydro-[1,1'-biphenyl]-3-yl)ethyl 2-methylbenzoate'
_chemical_properties_physical    Air-sensitive
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-21
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.9605(13)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.89050(7)
_cell_length_b                   23.7962(3)
_cell_length_c                   9.09712(12)
_cell_measurement_reflns_used    23509
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      32.7650
_cell_measurement_theta_min      2.8720
_cell_volume                     1242.67(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_details
;
  1 omega  -70.00  107.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       18.5695    0.0000 -120.0000 177

  2 omega  -14.00   95.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       18.5695   77.0000   30.0000 109

  3 omega  -14.00   95.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       18.5695   77.0000  -90.0000 109

  4 omega  -56.00   43.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       18.5695  -38.0000   30.0000 99

  5 omega  -80.00   -7.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -      -19.8195  133.0000   74.0000 73

  6 omega   34.00  106.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       18.5695 -178.0000   90.0000 72

  7 omega    7.00   79.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       18.5695 -133.0000    6.0000 72

  8 omega  -10.00   92.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -       18.5695   57.0000 -180.0000 102

  9 omega  -44.00   54.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -      -19.8195   38.0000 -180.0000 98

 10 omega -107.00  -34.00   1.0000   22.5000
omega____ theta____ kappa____ phi______ frames
    -      -19.8195  178.0000  150.0000 73
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0047798000
_diffrn_orient_matrix_UB_12      0.0226077000
_diffrn_orient_matrix_UB_13      0.0514085000
_diffrn_orient_matrix_UB_21      -0.0084711000
_diffrn_orient_matrix_UB_22      0.0194239000
_diffrn_orient_matrix_UB_23      -0.0601266000
_diffrn_orient_matrix_UB_31      -0.1231925000
_diffrn_orient_matrix_UB_32      -0.0004571000
_diffrn_orient_matrix_UB_33      -0.0118647000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            40829
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.960
_diffrn_reflns_theta_min         2.297
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.695
_exptl_absorpt_correction_T_max  0.993
_exptl_absorpt_correction_T_min  0.981
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'Clear yellowish'
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_F_000             556
_exptl_crystal_size_max          0.3046
_exptl_crystal_size_mid          0.1741
_exptl_crystal_size_min          0.1026
_refine_diff_density_max         3.236
_refine_diff_density_min         -0.795
_refine_diff_density_rms         0.119
_refine_ls_abs_structure_details
;
 Flack x determined using 3849 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.001(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     318
_refine_ls_number_reflns         8771
_refine_ls_number_restraints     268
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0491
_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^)+(0.0800P)^2^+1.8490P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1333
_refine_ls_wR_factor_ref         0.1355
_reflns_Friedel_coverage         0.922
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.923
_reflns_number_gt                8404
_reflns_number_total             8771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4cc08171d2.cif
_cod_data_source_block           exp_2279
_cod_database_code               7116104
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C27 H27 N2 O5 Br'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uiso(O1H) = Uiso(O1I)
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(O1I)=1-FVAR(1)
 Sof(O1H)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C11(H11), C12(H12)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C9(H9A,H9B), C19(H19A,H19B)
5.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C15(H15), C17(H17), N22(H22), C1E(H1E), C1G(H1G), C1K(H1K), C1M(H1M),
 C1Y(H1Y), C2(H2), C1(H1)
5.d Idealised Me refined as rotating group:
 C1C(H1CA,H1CB,H1CC), C1D(H1DA,H1DB,H1DC)
5.e Idealised tetrahedral OH refined as rotating group:
 O1P(H1P)
;
_shelx_res_checksum              25045
_olex2_submission_special_instructions 'No special instructions were received'