Lewis-Base-Catalyzed Asymmetric [3 + 3] Annulation Reaction of Morita–Baylis–Hillman Carbonates: Enantioselective Synthesis of Spirocyclohexenes
Yang, Wenjun; Sun, Wei; Zhang, Cheng; Wang, Qijun; Guo, Zhenyan; Mao, Biming; Liao, Jianning; Guo, Hongchao; ACS Catalysis 7 (2017) 3142–; doi:10.1021/acscatal.7b00320

data_4514169
_publ_section_title
;
 Lewis-Base-Catalyzed Asymmetric [3 + 3] Annulation Reaction of
 Morita--Baylis--Hillman Carbonates: Enantioselective Synthesis of
 Spirocyclohexenes
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              3142
_journal_paper_doi               10.1021/acscatal.7b00320
_journal_volume                  7
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C42 H29 Cl F6 N2 O3'
_chemical_formula_sum            'C42 H29 Cl F6 N2 O3'
_chemical_formula_weight         759.12
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-10-26
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9232(14)
_cell_length_b                   17.371(3)
_cell_length_c                   23.537(4)
_cell_measurement_reflns_used    9526
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4844
_cell_measurement_theta_min      1.4570
_cell_volume                     3648.4(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  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
scan:
    Number of images: 300
               Slice: -110.0000 - 40.0000
         Image width: 0.5000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 44.9338
              2theta: -19.7139
scan:
    Number of images: 300
               Slice: -110.0000 - 40.0000
         Image width: 0.5000
            Exp time: 6.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 44.9338
              2theta: -19.7139
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'MM007-HF CCD(Saturn 724+)'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0727
_diffrn_orient_matrix_UB_12      0.0827
_diffrn_orient_matrix_UB_13      0.0207
_diffrn_orient_matrix_UB_21      0.0282
_diffrn_orient_matrix_UB_22      0.0127
_diffrn_orient_matrix_UB_23      0.0486
_diffrn_orient_matrix_UB_31      0.0247
_diffrn_orient_matrix_UB_32      0.0271
_diffrn_orient_matrix_UB_33      -0.0214
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0417
_diffrn_reflns_av_unetI/netI     0.0447
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            24371
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.475
_diffrn_reflns_theta_min         1.730
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0000
_diffrn_source_power             1.2000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    0.178
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85068
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_description       block
_exptl_crystal_F_000             1560
_exptl_crystal_size_max          0.188
_exptl_crystal_size_mid          0.155
_exptl_crystal_size_min          0.104
_refine_diff_density_max         0.157
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 2444 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         8330
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0484
_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^)+(0.0350P)^2^+0.8443P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0952
_refine_ls_wR_factor_ref         0.0990
_reflns_Friedel_coverage         0.781
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                7472
_reflns_number_total             8330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b00320_si_002.cif
_cod_data_source_block           mx5239
_cod_depositor_comments          'Adding full bibliography for 4514169.cif.'
_cod_original_cell_volume        3648.4(10)
_cod_database_code               4514169
_diffrn_number_total             4707
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Others
 Sof(F6A)=Sof(F5A)=Sof(C42A)=1-FVAR(1)
 Sof(F5)=Sof(F6)=Sof(C42)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5)
3.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C34(H34A,H34B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C26(H26), C28(H28),
  C29(H29), C30(H30), C31(H31), C32(H32), C36(H36), C38(H38), C40(H40)
;
_shelx_res_checksum              18791
_shelx_hkl_checksum              85054
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'