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_1519944
_publ_section_title
;
 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         'C H2 Cl2, C34 H34 F12 N2 O6'
_chemical_formula_sum            'C35 H36 Cl2 F12 N2 O6'
_chemical_formula_weight         879.56
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-12-16
_audit_creation_method
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Olex2 1.2-beta
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4720)
;
_audit_update_record
;
2014-11-19 deposited with the CCDC.
2015-05-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.652(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.3901(7)
_cell_length_b                   13.5696(4)
_cell_length_c                   21.1866(6)
_cell_measurement_reflns_used    7984
_cell_measurement_temperature    180.1(5)
_cell_measurement_theta_max      72.5460
_cell_measurement_theta_min      3.9550
_cell_volume                     8136.1(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_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)
;
_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)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      180.1(5)
_diffrn_detector_area_resol_mean 10.4679
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0397855000
_diffrn_orient_matrix_UB_12      -0.0515961000
_diffrn_orient_matrix_UB_13      -0.0221090000
_diffrn_orient_matrix_UB_21      -0.0230967000
_diffrn_orient_matrix_UB_22      -0.1007036000
_diffrn_orient_matrix_UB_23      0.0045891000
_diffrn_orient_matrix_UB_31      -0.0290734000
_diffrn_orient_matrix_UB_32      0.0093713000
_diffrn_orient_matrix_UB_33      -0.0720824000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            15971
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.750
_diffrn_reflns_theta_max         72.571
_diffrn_reflns_theta_min         3.123
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.340
_exptl_absorpt_correction_T_max  0.873
_exptl_absorpt_correction_T_min  0.761
_exptl_absorpt_correction_type   analytical
_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)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.436
_exptl_crystal_description       block
_exptl_crystal_F_000             3600
_exptl_crystal_size_max          0.4301
_exptl_crystal_size_mid          0.1925
_exptl_crystal_size_min          0.1469
_refine_diff_density_max         1.522
_refine_diff_density_min         -0.984
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     598
_refine_ls_number_reflns         7836
_refine_ls_number_restraints     171
_refine_ls_restrained_S_all      1.158
_refine_ls_R_factor_all          0.0968
_refine_ls_R_factor_gt           0.0848
_refine_ls_shift/su_max          0.015
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1727P)^2^+10.4489P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2596
_refine_ls_wR_factor_ref         0.2851
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6433
_reflns_number_total             7836
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc01118c2.cif
_cod_data_source_block           macrocycle_8a
_cod_depositor_comments
'Adding full bibliography for 1519944--1519947.cif.'
_cod_original_cell_volume        8136.2(4)
_cod_database_code               1519944
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C35 H36 Cl2 F12 N2 O6'
_reflns_odcompleteness_completeness 99.53
_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 N(H) groups
2. Restrained distances
 C51-F52B \\sim C51-F52A \\sim C51-F54B \\sim C51-F54A \\sim F53B-C51 \\sim
F53A-C51
 with sigma of 0.02
 F52A-F53A \\sim F53A-F54A \\sim F54A-F52A
 with sigma of 0.04
 F52B-F53B \\sim F53B-F54B \\sim F54B-F52B
 with sigma of 0.04
 F35B-C33 \\sim F35A-C33 \\sim F34B-C33 \\sim F34A-C33 \\sim F36A-C33 \\sim
F36B-C33
 with sigma of 0.02
 F34A-F35A \\sim F35A-F36A \\sim F36A-F34A
 with sigma of 0.04
 F34B-F35B \\sim F35B-F36B \\sim F36B-F34B
 with sigma of 0.04
 F50B-C47 \\sim F50A-C47 \\sim F49B-C47 \\sim F49A-C47 \\sim F48A-C47 \\sim
F48B-C47
 with sigma of 0.02
 F48A-F49A \\sim F49A-F50A \\sim F50A-F48A
 with sigma of 0.04
 F48B-F49B \\sim F49B-F50B \\sim F50B-F48B
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 C51, F53A, F53B, F54A, F54B, F52B, F52A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F35B, F34B, F36B, C33, F36A, F35A, F34A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F48B, F50B, C47, F50A, F48A, F49B, F49A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F52A)=Sof(F53A)=Sof(F54A)=1-FVAR(1)
 Sof(F52B)=Sof(F53B)=Sof(F54B)=FVAR(1)
 Sof(F48B)=Sof(F49B)=Sof(F50B)=1-FVAR(2)
 Sof(F48A)=Sof(F49A)=Sof(F50A)=FVAR(2)
 Sof(F34B)=Sof(F35B)=Sof(F36B)=1-FVAR(3)
 Sof(F34A)=Sof(F35A)=Sof(F36A)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C11(H11)
5.b Secondary CH2 refined with riding coordinates:
 C100(H10C,H10D), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,
 H7B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,
 H17B)
5.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C30(H30), C32(H32), C42(H42), C44(H44), C46(H46), N23(H23), N26(H26)
5.d X=CH2 refined with riding coordinates:
 C10(H10A,H10B), C20(H20A,H20B)
;