Modular Chiral Bisoxalamide–Copper-Catalyzed Asymmetric Oxo-Diels–Alder Reaction: Carbonyl Coordination for High Enantio- and Diastereocontrols
Chen, Jun-Bo; Xu, Man; Zhang, Jun-Qi; Sun, Bing-Bing; Hu, Jia-Ming; Yu, Jie-Qiang; Wang, Xing-Wang; Xia, Yuanzhi; Wang, Zheng; ACS Catalysis  (2020) 3556–; doi:10.1021/acscatal.9b05606

data_4517456
_publ_section_title
;
 Modular Chiral Bisoxalamide--Copper-Catalyzed Asymmetric Oxo-Diels--Alder
 Reaction: Carbonyl Coordination for High Enantio- and Diastereocontrols
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              3556
_journal_paper_doi               10.1021/acscatal.9b05606
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C H2 Cl2, 2(C30 H42 N4 O4)'
_chemical_formula_sum            'C61 H86 Cl2 N8 O8'
_chemical_formula_weight         1130.27
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.8760(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.5285(4)
_cell_length_b                   16.5970(6)
_cell_length_c                   14.9439(5)
_cell_measurement_reflns_used    9963
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      27.20
_cell_measurement_theta_min      2.39
_cell_volume                     3100.26(18)
_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      120.01
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0649
_diffrn_reflns_av_unetI/netI     0.0611
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            53637
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.489
_diffrn_reflns_theta_min         1.629
_exptl_absorpt_coefficient_mu    0.163
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_description       block
_exptl_crystal_F_000             1212
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.571
_refine_diff_density_min         -0.582
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 4384 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     740
_refine_ls_number_reflns         14166
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0403P)^2^+1.6150P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1089
_refine_ls_wR_factor_ref         0.1252
_reflns_Friedel_coverage         0.927
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                11185
_reflns_number_total             14166
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b05606_si_003.cif
_cod_data_source_block           20181112b
_cod_database_code               4517456
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.953
_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 C(H,H,H,H,H,H) groups
2. Restrained distances
 C42A-C41 \\sim C42-C41
 with sigma of 0.02
 N6-C44A \\sim N6-C44
 with sigma of 0.02
 C45-C44A \\sim C45-C44 \\sim C46-C44
 with sigma of 0.02
 C45-C46 \\sim C45-C46A
 with sigma of 0.02
 N6-C46 \\sim N6-C46A
 with sigma of 0.02
 C40-C44 \\sim C40-C44A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C42A) = Uanis(C42)
Uanis(C46A) = Uanis(C46)
Uanis(C44A) = Uanis(C44)
4. Rigid body (RIGU) restrains
 C44, C44A, C46A, C46, C42A, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H41A)=Sof(C44A)=Sof(H44A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C42A)=
 Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C46A)=Sof(H46D)=Sof(H46E)=Sof(H46F)=1-FVAR(1)
 Sof(H41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C44)=Sof(H44)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C2(H2), C11(H11), C14(H14), C25(H25), C28(H28), C31(H31), C32(H32),
 C41(H41), C41(H41A), C44A(H44A), C55(H55), C58(H58), C44(H44)
6.b Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), C4(H4), C5(H5A), C6(H6), C7(H7A), C8(H8), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), N5(H5), N7(H7), C34(H34), C35(H35), C36(H36),
 C37(H37), C38(H38), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52)
6.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45D,H45E,H45F),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C42A(H42D,H42E,H42F),
 C46A(H46D,H46E,H46F)
;
_shelx_res_checksum              91026
_shelx_hkl_checksum              6315
_olex2_submission_special_instructions 'No special instructions were received'