Remote stereoselective deconjugation of α,β-unsaturated esters by simple amidation reactions
Vishe, Mahesh; Hrdina, Radim; Poblador-Bahamonde, Amalia I.; Besnard, Céline; Guénée, Laure; Bürgi, Thomas; Lacour, Jérôme; Chem. Sci. 6 (2015) 4923–; doi:10.1039/C5SC01118C

data_1519945
_publ_section_title
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 Remote stereoselective deconjugation of \a,\b-unsaturated esters by
 simple amidation reactions
;
_journal_issue                   8
_journal_name_full               'Chem. Sci.'
_journal_page_first              4923
_journal_paper_doi               10.1039/C5SC01118C
_journal_volume                  6
_journal_year                    2015
_chemical_formula_moiety         'C26 H32 N4 O8, H2 O, 1(C7 H8)'
_chemical_formula_sum            'C33 H42 N4 O9'
_chemical_formula_weight         638.70
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-01-23
_audit_creation_method
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Olex2 1.2-beta
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
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_audit_update_record
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2014-11-19 deposited with the CCDC.
2015-05-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.8170(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.43180(15)
_cell_length_b                   18.5656(3)
_cell_length_c                   17.6555(3)
_cell_measurement_reflns_used    7595
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      72.4160
_cell_measurement_theta_min      3.4380
_cell_volume                     3419.04(9)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
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_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      180.15
_diffrn_detector_area_resol_mean 10.4679
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1396157000
_diffrn_orient_matrix_UB_12      0.0189222000
_diffrn_orient_matrix_UB_13      -0.0191230000
_diffrn_orient_matrix_UB_21      -0.0480602000
_diffrn_orient_matrix_UB_22      0.0571509000
_diffrn_orient_matrix_UB_23      -0.0569249000
_diffrn_orient_matrix_UB_31      0.0018435000
_diffrn_orient_matrix_UB_32      0.0571036000
_diffrn_orient_matrix_UB_33      0.0633436000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0162
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_laue_measured_fraction_full 0.998
_diffrn_reflns_laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            13891
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.537
_diffrn_reflns_theta_min         3.455
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.751
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72469
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.241
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.8092
_exptl_crystal_size_mid          0.4242
_exptl_crystal_size_min          0.1313
_refine_diff_density_max         0.228
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.032
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     521
_refine_ls_number_reflns         6622
_refine_ls_number_restraints     299
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0377
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1295
_refine_ls_wR_factor_ref         0.1370
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5819
_reflns_number_total             6622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc01118c2.cif
_cod_data_source_block           macrocycle_4l
_cod_depositor_comments
'Adding full bibliography for 1519944--1519947.cif.'
_cod_original_cell_volume        3419.05(8)
_cod_database_code               1519945
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'Fe Co C72 N16 O20 H60 Cl4'
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O5-C4 \\sim O5D-C4D \\sim O5-C6 \\sim O5D-C6
 with sigma of 0.02
 C4-C3 \\sim C4D-C3D
 with sigma of 0.02
 O2-C3 \\sim O2-C3D
 with sigma of 0.02
 C4-O2 \\sim O2-C4D
 with sigma of 0.04
 C3D-O5D \\sim C3-O5
 with sigma of 0.04
 C4-C6 \\sim C6-C4D
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C6B \\sim C1B \\sim C2B \\sim C3 \\sim C7B \\sim C4 \\sim C5B \\sim C6C \\sim
C1C \\sim C2C \\sim C7C \\sim C3C \\sim C4C \\sim C5C \\sim C2A \\sim C1A \\sim
C7A \\sim C3A \\sim C6A \\sim C4D \\sim C5A: within 1.1A with sigma of 0.04 and
sigma for terminal atoms of 0.08
O5D \\sim O5 \\sim C4 \\sim C4D \\sim C3D \\sim C3: within 1.1A with sigma of
0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 C2A, C1A, C7A, C3A, C6A, C4D, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6B, C1B, C2B, C3, C7B, C4, C5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6C, C1C, C2C, C7C, C3C, C4C, C5C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6, O5D, C4D, C3D, O2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C3, C4, O5, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H6BC)=Sof(H6BD)=1-FVAR(1)
 Sof(H6AA)=Sof(H6AB)=FVAR(1)
 Fixed Sof: O5(0.46919) C3(0.46919) H3A(0.46919) H3B(0.46919) C4(0.46919)
 H4A(0.46919) H4B(0.46919) C1B(0.37) H1BA(0.37) H1BB(0.37) H1BC(0.37) C2B(0.37)
 C3B(0.37) H3BA(0.37) C4B(0.37) H4BA(0.37) C5B(0.37) H5B(0.37) C6B(0.37)
 H6B(0.37) C7B(0.37) H7BA(0.37) C1C(0.35) H1CA(0.35) H1CB(0.35) H1CC(0.35)
 C2C(0.35) C7C(0.35) H7C(0.35) C6C(0.35) H6C(0.35) C5C(0.35) H5C(0.35)
 C4C(0.35) H4C(0.35) C3C(0.35) H3C(0.35) C4D(0.53081) H4DA(0.53081)
 H4DB(0.53081) C3D(0.53081) H3DA(0.53081) H3DB(0.53081) C1A(0.28) H1AA(0.28)
 H1AB(0.28) H1AC(0.28) C2A(0.28) C7A(0.28) H7AA(0.28) C6A(0.28) H6A(0.28)
 C5A(0.28) H5A(0.28) C4A(0.28) H4AA(0.28) C3A(0.28) H3AA(0.28) O5D(0.53081)
6.a Free rotating group:
 OW1(HW1A,HW1B), C1B(C2B,C3B,C4B,C5B,C6B,C7B), C1C(C2C,C7C,C6C,C5C,C4C,C3C,C4D,
 C3D), C1A(C2A,C7A,C6A,C5A,C4A,C3A,O5D)
6.b Ternary CH refined with riding coordinates:
 C18(H18), C9(H9)
6.c Secondary CH2 refined with riding coordinates:
 C6(H6BC,H6BD), C6(H6AA,H6AB), C15(H15A,H15B), C16(H16A,H16B), C12(H12A,H12B),
 C7(H7A,H7B), C3(H3A,H3B), C13(H13A,H13B), C4(H4A,H4B), C4D(H4DA,H4DB),
 C3D(H3DA,H3DB)
6.d Aromatic/amide H refined with riding coordinates:
 N32(H32), N23(H23), C34(H34), C38(H38), C29(H29), C28(H28), C25(H25),
 C35(H35), C37(H37), C26(H26), C3B(H3BA), C4B(H4BA), C5B(H5B), C6B(H6B),
 C7B(H7BA), C7C(H7C), C6C(H6C), C5C(H5C), C4C(H4C), C3C(H3C), C7A(H7AA),
 C6A(H6A), C5A(H5A), C4A(H4AA), C3A(H3AA)
6.e X=CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B)
6.f Idealised Me refined as rotating group:
 C1B(H1BA,H1BB,H1BC), C1C(H1CA,H1CB,H1CC), C1A(H1AA,H1AB,H1AC)
;