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_7156938
_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_formula_moiety         'C30 H38 N2 Na O8, C32 H12 B F24'
_chemical_formula_sum            'C62 H50 B F24 N2 Na O8'
_chemical_formula_weight         1440.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-06-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-14 deposited with the CCDC.    2019-06-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.8737(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.7333(3)
_cell_length_b                   20.1120(3)
_cell_length_c                   18.2281(3)
_cell_measurement_reflns_used    12995
_cell_measurement_temperature    180.05(10)
_cell_measurement_theta_max      73.2310
_cell_measurement_theta_min      3.9850
_cell_volume                     6486.24(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      N~2~
_diffrn_ambient_temperature      180.05(10)
_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 0.974
_diffrn_measurement_details
;
  1 omega  -45.00   34.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365   38.0000   90.0000 79

  2 omega  -51.00    5.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365   19.0000    0.0000 56

  3 omega   57.00  126.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000   90.0000 69

  4 omega   85.00  114.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000  150.0000 29

  5 omega   90.00  175.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   30.0000   60.0000 85

  6 omega   61.00   87.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -30.0000 -180.0000 26

  7 omega   30.00  116.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499 -111.0000  -30.0000 86

  8 omega   42.00  136.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -61.0000   60.0000 94

  9 omega   43.00   69.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -30.0000  120.0000 26

 10 omega   34.00   91.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -30.0000  150.0000 57

 11 omega   28.00   89.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000    0.0000 61

 12 omega  120.00  150.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  178.0000 -180.0000 30

 13 omega   57.00  101.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  178.0000 -180.0000 44

 14 omega -123.00  -84.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -99.0000   60.0000 39
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0118306000
_diffrn_orient_matrix_UB_12      -0.0758738000
_diffrn_orient_matrix_UB_13      0.0046465000
_diffrn_orient_matrix_UB_21      -0.0573417000
_diffrn_orient_matrix_UB_22      -0.0093782000
_diffrn_orient_matrix_UB_23      -0.0665848000
_diffrn_orient_matrix_UB_31      0.0644965000
_diffrn_orient_matrix_UB_32      0.0053563000
_diffrn_orient_matrix_UB_33      -0.0520551000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0233
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26287
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         73.648
_diffrn_reflns_theta_min         3.327
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.327
_exptl_absorpt_correction_T_max  0.801
_exptl_absorpt_correction_T_min  0.545
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.475
_exptl_crystal_description       prism
_exptl_crystal_F_000             2928
_exptl_crystal_size_max          0.6999
_exptl_crystal_size_mid          0.4418
_exptl_crystal_size_min          0.1806
_refine_diff_density_max         1.390
_refine_diff_density_min         -0.973
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     911
_refine_ls_number_reflns         12752
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0820
_refine_ls_R_factor_gt           0.0747
_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^)+(0.1180P)^2^+5.8410P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2070
_refine_ls_wR_factor_ref         0.2163
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11018
_reflns_number_total             12752
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob01355e2.cif
_cod_data_source_block           Na-3a-BArF
_cod_depositor_comments
'Adding full bibliography for 7156936--7156938.cif.'
_cod_database_code               7156938
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C62 H50 B F24 N2 Na O8'
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
Uanis(F1B) = Uanis(F1A) = Uanis(F2A) = Uanis(F2B) = Uanis(F3A) = Uanis(F3B)
Uanis(F16A) = Uanis(F16B)
Uanis(F18A) = Uanis(F18B)
Uanis(F17A) = Uanis(F17B)
Uanis(F12B) = Uanis(F12A)
Uanis(F10B) = Uanis(F10A)
Uanis(F11B) = Uanis(F11A)
Uanis(F8B) = Uanis(F8A)
Uanis(F9B) = Uanis(F9A)
Uanis(F7B) = Uanis(F7A)
3. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(1)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=1-FVAR(2)
 Sof(F17A)=Sof(F16A)=Sof(F18A)=FVAR(2)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(3)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(3)
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(4)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(4)
4.a Ternary CH refined with riding coordinates:
 C11(H11), C21(H21)
4.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B), C19(H19A,H19B),
 C25(H25A,H25B), C26(H26A,H26B), C28(H28A,H28B), C29(H29A,H29B), C33(H33A,H33B)
4.c Aromatic/amide H refined with riding coordinates:
 N8(H8), N32(H32), C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C35(H35), C36(H36),
 C37(H37), C38(H38), C39(H39), C41(H41), C43(H43), C45(H45), C49(H49), C51(H51),
  C53(H53), C57(H57), C59(H59), C61(H61), C66(H66), C68(H68), C70(H70)
4.d X=CH2 refined with riding coordinates:
 C13(H13A,H13B), C23(H23A,H23B)
;
_shelx_res_checksum              9814
_shelx_hkl_checksum              17370
_olex2_submission_special_instructions 'No special instructions were received'