Organocatalytic Enantioselective [1 + 4] Annulation of Morita-Baylis-Hillman Carbonates with Electron-Deficient Olefins: Access to Chiral 2,3-Dihydrofuran Derivatives.
Cheng, Yuyu; Han, Yuzhe; Li, Pengfei; Organic letters 19 (2017) 4774–4777; doi:10.1021/acs.orglett.7b02144

data_1547555
_publ_section_title
;
 Organocatalytic Enantioselective [1 + 4] Annulation of
 Morita-Baylis-Hillman Carbonates with Electron-Deficient Olefins: Access
 to Chiral 2,3-Dihydrofuran Derivatives.
;
_journal_issue                   18
_journal_name_full               'Organic letters'
_journal_page_first              4774
_journal_page_last               4777
_journal_paper_doi               10.1021/acs.orglett.7b02144
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H23 Br O3'
_chemical_formula_sum            'C23 H23 Br O3'
_chemical_formula_weight         427.32
_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     dual
_audit_creation_date             2017-04-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.2570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.5574(2)
_cell_length_b                   11.2786(4)
_cell_length_c                   16.5421(6)
_cell_measurement_reflns_used    9192
_cell_measurement_temperature    150
_cell_measurement_theta_max      68.50
_cell_measurement_theta_min      4.77
_cell_volume                     1023.35(6)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20365
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.615
_diffrn_reflns_theta_min         4.765
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.891
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5285
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1003 before and 0.0474 after correction. The Ratio of minimum to maximum transmission is 0.7018. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.387
_exptl_crystal_description       block
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.410
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 1643 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.033(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.133
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3707
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.0359
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0560P)^2^+0.5676P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.0990
_reflns_Friedel_coverage         0.885
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                3606
_reflns_number_total             3707
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02144_si_002.cif
_cod_data_source_block           cu_cxy0015_0m
_cod_database_code               1547555
_shelx_shelxl_version_number     2016/6
_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
 C4-C2 = C4A-C2A = C2A-C1A = C2-C1 = C3A-C2A = C3-C2
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3A) \\sim
Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C4) = Uanis(C4A)
Uanis(C2) = Uanis(C2A)
Uanis(C3) = Uanis(C3A)
Uanis(C1) = Uanis(C1A)
Uanis(O3) = Uanis(O3A)
4. Others
 Sof(O3A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C2A)=Sof(H2A)=Sof(C3A)=
 Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=1-FVAR(1)
 Sof(O3)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9), C2(H2), C2A(H2A)
5.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C4A(H4AA,H4AB)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19),
 C20(H20), C22(H22), C23(H23)
5.d X=CH2 refined with riding coordinates:
 C7(H7A,H7B)
5.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C1A(H1AA,H1AB,H1AC), C3A(H3AA,H3AB,H3AC)
;
_shelx_res_checksum              66335
_shelx_hkl_checksum              32879
_olex2_submission_special_instructions 'No special instructions were received'