Phosphine-Catalyzed Highly Enantioselective [3 + 3] Cycloaddition of Morita-Baylis-Hillman Carbonates with C,N-Cyclic Azomethine Imines.
Zhang, Lei; Liu, Honglei; Qiao, Guanyu; Hou, Zhanfeng; Liu, Yang; Xiao, Yumei; Guo, Hongchao; Journal of the American Chemical Society  (2015) 150327094845007–; doi:10.1021/jacs.5b01138

data_4123541
_publ_section_title
;
 Phosphine-Catalyzed Highly Enantioselective [3 + 3] Cycloaddition of
 Morita-Baylis-Hillman Carbonates with C,N-Cyclic Azomethine Imines.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              150327094845007
_journal_paper_doi               10.1021/jacs.5b01138
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H24 Cl2 N2 O4 S'
_chemical_formula_sum            'C27 H24 Cl2 N2 O4 S'
_chemical_formula_weight         543.44
_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   mixed
_audit_creation_date             2014-12-30
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.349(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.181(3)
_cell_length_b                   11.497(3)
_cell_length_c                   19.231(5)
_cell_measurement_reflns_used    8737
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4715
_cell_measurement_theta_min      1.1156
_cell_volume                     2556.3(11)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2013)'
_computing_structure_solution
;
'SHELXS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0496
_diffrn_orient_matrix_UB_12      0.0696
_diffrn_orient_matrix_UB_13      -0.0135
_diffrn_orient_matrix_UB_21      -0.0072
_diffrn_orient_matrix_UB_22      -0.0214
_diffrn_orient_matrix_UB_23      -0.0840
_diffrn_orient_matrix_UB_31      -0.0523
_diffrn_orient_matrix_UB_32      -0.0143
_diffrn_orient_matrix_UB_33      0.0081
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0328
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            28034
_diffrn_reflns_point_group_measured_fraction_full 0.948
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.505
_diffrn_reflns_theta_min         1.116
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.373
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8636
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_description       block
_exptl_crystal_F_000             1128
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.23
_refine_diff_density_max         0.239
_refine_diff_density_min         -0.282
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 4488 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.019(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     690
_refine_ls_number_reflns         10918
_refine_ls_number_restraints     143
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0334
_refine_ls_R_factor_gt           0.0326
_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^)+(0.0294P)^2^+0.6326P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0723
_refine_ls_wR_factor_ref         0.0729
_reflns_Friedel_coverage         0.792
_reflns_Friedel_fraction_full    0.897
_reflns_Friedel_fraction_max     0.868
_reflns_number_gt                10735
_reflns_number_total             10918
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01138_si_002.cif
_cod_data_source_block           sa3823
_cod_original_cell_volume        2556.4(11)
_cod_database_code               4123541
_shelxl_version_number           2013-4
_diffrn_number_total             6111
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C23B-C22A = C24B-C23B = C25B-C24B = C26A-C25B
 1.39 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C23A \\sim C24A \\sim C25A \\sim C27A \\sim C25B \\sim C24B \\sim C23B \\sim
C27B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C27A) \\sim Ueq, Uanis(C27B) \\sim Ueq, Uanis(C24B) \\sim Ueq,
Uanis(C24A) \\sim Ueq, Uanis(C25B) \\sim Ueq, Uanis(C25A) \\sim Ueq,
Uanis(C23A) \\sim Ueq, Uanis(C23B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(H22B)=Sof(H26B)=Sof(C25B)=Sof(H25B)=Sof(C24B)=Sof(C23B)=Sof(H23B)=
 Sof(C27B)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(1)
 Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(C25A)=Sof(H25A)=Sof(H26A)=
 Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(1)
5.a Riding coordinates:
 C27B(H27D,H27E,H27F)
5.b Ternary CH refined with riding coordinates:
 C1A(H1A), C2A(H2A), C1(H1), C2(H2)
5.c Secondary CH2 refined with riding coordinates:
 C5A(H5AA,H5AB), C6A(H6AA,H6AB), C5(H5A,H5B), C6(H6A,H6B)
5.d Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C14A(H14A), C16A(H16A),
 C18A(H18A), C22A(H22A), C22A(H22B), C23A(H23A), C25A(H25A), C26A(H26A),
 C26A(H26B), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C16(H16),
 C18(H18), C22(H22), C23(H23), C25(H25), C26(H26), C25B(H25B), C23B(H23B)
5.e Idealised Me refined as rotating group:
 C20A(H20A,H20B,H20C), C27A(H27A,H27B,H27C), C20(H20D,H20E,H20F), C27(H27G,
 H27H,H27I)
;
_shelx_res_checksum              41778
_shelx_hkl_checksum              91760