Asymmetric conjugate additions of 2-substituted benzofuran-3(2H)-ones to α,β-unsaturated ketones catalyzed by chiral copper complexes
Wang, Haojiang; Wang, Yifeng; Zhang, Cheng; Jiang, Yidong; Chu, Mingming; Li, Zhaobo; Du, Xiaohua; Xu, Danqian; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB00677B

data_7155596
_publ_section_title
;
 Asymmetric conjugate additions of 2-substituted benzofuran-3(2H)-ones to
 \a,\b-unsaturated ketones catalyzed by chiral copper complexes
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB00677B
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_compound_source        'organic synthesis'
_chemical_formula_moiety         'C15 H15 Cl O5'
_chemical_formula_sum            'C15 H15 Cl O5'
_chemical_formula_weight         310.72
_chemical_melting_point          135
_chemical_name_common
'methyl 5-chloro-3-oxo-2-(4-oxopentan-2-yl)-2,3-dihydrobenzofuran-2-carboxylate'
_chemical_name_systematic
'methyl 5-chloro-3-oxo-2-(4-oxopentan-2-yl)-2,3-dihydrobenzofuran-2-carboxylate'
_chemical_properties_physical    ', Heat-sensitive'
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_symmetry_space_group_name_Hall  'P 65'
_symmetry_space_group_name_H-M   'P 65'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2016-12-20
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_audit_update_record
;
2016-12-21 deposited with the CCDC.
2017-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   15.8422(17)
_cell_length_b                   15.8422(17)
_cell_length_c                   11.1926(12)
_cell_measurement_reflns_used    2533
_cell_measurement_temperature    130
_cell_measurement_theta_max      20.487
_cell_measurement_theta_min      2.35
_cell_volume                     2432.7(5)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0768
_diffrn_reflns_av_unetI/netI     0.0625
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            20466
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_theta_min         1.48
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.252
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6540
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0618 before and 0.0544 after correction.
The Ratio of minimum to maximum transmission is 0.8771.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.273
_exptl_crystal_description       block
_exptl_crystal_F_000             972
_exptl_crystal_preparation       ', Luminescent'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichoromethane'
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.232
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 939 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.924
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     322
_refine_ls_number_reflns         3011
_refine_ls_number_restraints     265
_refine_ls_restrained_S_all      0.918
_refine_ls_R_factor_all          0.0719
_refine_ls_R_factor_gt           0.0535
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1454P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1541
_refine_ls_wR_factor_ref         0.1733
_reflns_Friedel_coverage         0.895
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                2490
_reflns_number_total             3011
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00677b2.cif
_cod_data_source_block           mo_dm16873_0m
_cod_original_cell_volume        2432.7(6)
_cod_database_code               7155596
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.988
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.577(9) 0.423(9)
2. 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
3. Restrained distances
 C10-C9
 1.59 with sigma of 0.02
 C1-C9 = C11-C9 = C10-C9 = C1-C14
 1.59 with sigma of 0.02
 O1-C1 = O1-C8 = O4-C15
 1.48 with sigma of 0.02
 C9-C1 = C14-C1
 1.59 with sigma of 0.02
 C2-C1 = C2-C3
 1.59 with sigma of 0.02
 C9-C11
 1.59 with sigma of 0.02
 O2-C2 = C14-O4 = C14-O3
 1.28 with sigma of 0.01
 C9'-C10'
 1.58 with sigma of 0.01
 O4'-C15'
 1.48 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C1 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01
C1' \\sim O4' \\sim O3' \\sim C14': within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C15) \\sim
Ueq, Uanis(C9) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(C9') \\sim Ueq, Uanis(C14') \\sim Ueq, Uanis(O3') \\sim Ueq, Uanis(O4')
\\sim Ueq, Uanis(C15') \\sim Ueq, Uanis(O2') \\sim Ueq, Uanis(C2') \\sim Ueq,
Uanis(C1') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C10) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(O3)
\\sim Ueq, Uanis(O1') \\sim Ueq, Uanis(O3') \\sim Ueq, Uanis(O4') \\sim Ueq,
Uanis(O2') \\sim Ueq, Uanis(C2') \\sim Ueq, Uanis(C9') \\sim Ueq, Uanis(C10')
\\sim Ueq, Uanis(C14') \\sim Ueq, Uanis(C15') \\sim Ueq: with sigma of 0.002
and sigma for terminal atoms of 0.004
Uanis(C9') \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C15') \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O3') \\sim Ueq, Uanis(C11') \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O3') \\sim Ueq, Uanis(O5) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C5) \\sim Ueq, Uanis(O2') \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
5. Others
 Fixed Sof: O1(0.5) O2(0.5) O3(0.5) O4(0.5) O5(0.5) O1'(0.5) O2'(0.5) O3'(0.5)
 O4'(0.5) O5'(0.5) C1(0.5) C2(0.5) H3(0.5) H7(0.5) C9(0.5) H9(0.5) C10(0.5)
 H10A(0.5) H10B(0.5) H10C(0.5) C11(0.5) H11A(0.5) H11B(0.5) C12(0.5) C13(0.5)
 H13A(0.5) H13B(0.5) H13C(0.5) C14(0.5) C15(0.5) H15A(0.5) H15B(0.5) H15C(0.5)
 C1'(0.5) C2'(0.5) C9'(0.5) H9'(0.5) C10'(0.5) H10D(0.5) H10E(0.5) H10F(0.5)
 C11'(0.5) H11C(0.5) H11D(0.5) C12'(0.5) C13'(0.5) H13D(0.5) H13E(0.5)
 H13F(0.5) C14'(0.5) C15'(0.5) H15D(0.5) H15E(0.5) H15F(0.5)
6.a Riding coordinates:
 C15(H15A,H15B,H15C)
6.b Ternary CH refined with riding coordinates:
 C9(H9), C9'(H9')
6.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C11'(H11C,H11D)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7)
6.e Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C13(H13A,H13B,H13C), C10'(H10D,H10E,H10F), C13'(H13D,
 H13E,H13F), C15'(H15D,H15E,H15F)
;
_shelx_res_checksum              11153
_shelx_hkl_checksum              40497
_shelx_fab_checksum              3441
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'