Stereoselective deconjugation of macrocyclic α,β-unsaturated esters by sequential amidation and olefin transposition: application to enantioselective phase-transfer catalysis.
Homberg, Alexandre; Hrdina, Radim; Vishe, Mahesh; Guénée, Laure; Lacour, Jérôme; Organic & biomolecular chemistry 17 (2019) 6905–6910; doi:10.1039/c9ob01355e

data_7156937
_publ_section_title
;
 Stereoselective deconjugation of macrocyclic \a,\b-unsaturated esters by
 sequential amidation and olefin transposition: application to
 enantioselective phase-transfer catalysis.
;
_journal_issue                   28
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              6905
_journal_page_last               6910
_journal_paper_doi               10.1039/c9ob01355e
_journal_volume                  17
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C40 H46 N2 Na O8, C32 H12 B F24'
_chemical_formula_sum            'C72 H58 B F24 N2 Na O8'
_chemical_formula_weight         1569.00
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-04-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_audit_update_record
;
2019-06-14 deposited with the CCDC.    2019-06-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.8583(7)
_cell_length_b                   19.3929(5)
_cell_length_c                   19.5642(7)
_cell_measurement_reflns_used    8184
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      73.7440
_cell_measurement_theta_min      3.1610
_cell_volume                     7155.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (Rigaku OD, 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    'ShelXS (Sheldrick, 2015)'
_diffrn_ambient_temperature      180.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -60.00  42.00   1.00    4.00    --  -37.69  38.00 -60.00  102
  2  \w     25.00  52.00   1.00    4.00    --   37.69  38.00-180.00   27
  3  \w     22.00  79.00   1.00    4.00    --   37.69 -99.00-120.00   57
  4  \w     36.00 146.00   1.00   16.00    --  110.40 -30.00-120.00  110
  5  \w    103.00 175.00   1.00   16.00    --  110.40 111.00-180.00   72
  6  \w     31.00 114.00   1.00   16.00    --  110.40-111.00 150.00   83
  7  \w    125.00 172.00   1.00   16.00    --  110.40 111.00-150.00   47
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0506252000
_diffrn_orient_matrix_UB_12      0.0052832000
_diffrn_orient_matrix_UB_13      -0.0615966000
_diffrn_orient_matrix_UB_21      0.0632189000
_diffrn_orient_matrix_UB_22      -0.0098075000
_diffrn_orient_matrix_UB_23      -0.0489894000
_diffrn_orient_matrix_UB_31      -0.0111503000
_diffrn_orient_matrix_UB_32      -0.0785661000
_diffrn_orient_matrix_UB_33      0.0020436000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0448
_diffrn_reflns_av_unetI/netI     0.0604
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18332
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         73.620
_diffrn_reflns_theta_min         3.209
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.254
_exptl_absorpt_correction_T_max  0.917
_exptl_absorpt_correction_T_min  0.772
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
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)
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    1.457
_exptl_crystal_description       prism
_exptl_crystal_F_000             3200
_exptl_crystal_size_max          0.358
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.085
_refine_diff_density_max         0.906
_refine_diff_density_min         -0.611
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.19(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     961
_refine_ls_number_reflns         12202
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0993
_refine_ls_R_factor_gt           0.0823
_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^)+(0.1298P)^2^+4.7363P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2183
_refine_ls_wR_factor_ref         0.2426
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                9600
_reflns_number_total             12202
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01355e2.cif
_cod_data_source_block           Na-SSSS-3n-BArF
_cod_depositor_comments
'Adding full bibliography for 7156936--7156938.cif.'
_cod_database_code               7156937
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C72 H58 B F24 N2 Na O8'
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.19(19)
 -0.19(19)
2. 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
3. Uiso/Uaniso restraints and constraints
Uiso(F4B) = Uiso(F4A)
Uiso(F5B) = Uiso(F5A)
Uiso(F6A) = Uiso(F6B)
Uiso(F21A) = Uiso(F21B)
Uiso(F20A) = Uiso(F20B)
Uiso(F19A) = Uiso(F19B)
Uiso(F14B) = Uiso(F14A)
Uiso(F13B) = Uiso(F13A)
Uiso(F15B) = Uiso(F15A)
4. Others
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(1)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=1-FVAR(2)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(2)
 Sof(F13B)=Sof(F14B)=Sof(F15B)=1-FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C11(H11), C24(H24), C39(H39)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), C15(H15A,H15B), C16(H16A,
 H16B), C18(H18A,H18B), C19(H19A,H19B)
5.c Aromatic/amide H refined with riding coordinates:
 N23(H23), N38(H38), C27(H27), C28(H28), C29(H29), C31(H31), C32(H32),
 C33(H33), C34(H34), C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48),
  C49(H49), C52(H52), C54(H54), C56(H56), C60(H60), C62(H62), C64(H64),
 C68(H68), C70(H70), C72(H72), C76(H76), C78(H78), C80(H80)
5.d X=CH2 refined with riding coordinates:
 C3(H3A,H3B), C13(H13A,H13B)
5.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              79848
_shelx_hkl_checksum              59051
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.456
_oxdiff_exptl_absorpt_empirical_full_min 0.542