Photo-induced thiol-ene reactions for late-stage functionalization of unsaturated polyether macrocycles: regio and diastereoselective access to macrocyclic dithiol derivatives.
Brun, Elodie; Zhang, Ke-Feng; Guénée, Laure; Lacour, Jérôme; Organic & biomolecular chemistry 18 (2020) 250–254; doi:10.1039/c9ob02375e

data_7157285
_publ_section_title
;
 Photo-induced thiol-ene reactions for late-stage functionalization of
 unsaturated polyether macrocycles: regio and diastereoselective access to
 macrocyclic dithiol derivatives.
;
_journal_issue                   2
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              250
_journal_page_last               254
_journal_paper_doi               10.1039/c9ob02375e
_journal_volume                  18
_journal_year                    2020
_chemical_formula_moiety         'C32 H34 F12 N2 O8 S2'
_chemical_formula_sum            'C32 H34 F12 N2 O8 S2'
_chemical_formula_weight         866.73
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-26
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2019-09-09 deposited with the CCDC.	2019-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                83.763(5)
_cell_angle_beta                 77.823(5)
_cell_angle_gamma                73.022(5)
_cell_formula_units_Z            2
_cell_length_a                   9.8217(5)
_cell_length_b                   10.9991(7)
_cell_length_c                   18.8342(12)
_cell_measurement_reflns_used    4730
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      73.6230
_cell_measurement_theta_min      4.1670
_cell_volume                     1899.8(2)
_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 0.998
_diffrn_measured_fraction_theta_max 0.969
_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    -68.00  23.00   1.00    2.50    --  -37.69  57.00-180.00   91
  2  \w   -101.00  -6.00   1.00    2.50    --  -37.69 -38.00   0.00   95
  3  \w   -109.00  -8.00   1.00    2.50    --  -37.69 -38.00 -90.00  101
  4  \w     97.00 130.00   1.00    2.50    --   37.69 178.00  90.00   33
  5  \w    122.00 147.00   1.00   10.00    --  110.40  61.00  90.00   25
  6  \w     82.00 158.00   1.00   10.00    --  110.40  45.00  30.00   76
  7  \w     81.00 107.00   1.00   10.00    --  110.40  61.00  90.00   26
  8  \w     34.00 115.00   1.00   10.00    --  110.40 -61.00  90.00   81
  9  \w     78.00 115.00   1.00   10.00    --  110.40-111.00   0.00   37
 10  \w     65.00 108.00   1.00   10.00    --  110.40 -94.00  60.00   43
 11  \w     49.00 139.00   1.00   10.00    --  110.40 -61.00 -60.00   90
 12  \w     89.00 135.00   1.00   10.00    --  110.40 -45.00-150.00   46
 13  \w    138.00 169.00   1.00   10.00    --  110.40  30.00-120.00   31
 14  \w     74.00 111.00   1.00   10.00    --  110.40  30.00-120.00   37
 15  \w     53.00 153.00   1.00   10.00    --  110.40  15.00-180.00  100
 16  \w     76.00 107.00   1.00   10.00    --  110.40-111.00-168.00   31
 17  \w     42.00  68.00   1.00   10.00    --  110.40-111.00-168.00   26
 18  \w     35.00 109.00   1.00   10.00    --  110.40 -94.00-120.00   74
 19  \w     32.00  78.00   1.00   10.00    --  110.40 -45.00-150.00   46
 20  \w     30.00  65.00   1.00   10.00    --  110.40-111.00 -30.00   35
 21  \w   -127.00 -37.00   1.00    2.50    --  -37.69 178.00 150.00   90
;
_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      0.0176281000
_diffrn_orient_matrix_UB_12      -0.1288308000
_diffrn_orient_matrix_UB_13      0.0434954000
_diffrn_orient_matrix_UB_21      -0.0082202000
_diffrn_orient_matrix_UB_22      0.0658079000
_diffrn_orient_matrix_UB_23      0.0695445000
_diffrn_orient_matrix_UB_31      -0.1658582000
_diffrn_orient_matrix_UB_32      0.0239303000
_diffrn_orient_matrix_UB_33      0.0170765000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0230
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            12306
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         73.628
_diffrn_reflns_theta_min         4.208
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.273
_exptl_absorpt_correction_T_max  0.956
_exptl_absorpt_correction_T_min  0.710
_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    1.515
_exptl_crystal_description       plate
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.656
_refine_diff_density_min         -0.616
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         7433
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0745
_refine_ls_R_factor_gt           0.0590
_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^)+(0.0710P)^2^+1.4660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1536
_refine_ls_wR_factor_ref         0.1696
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5808
_reflns_number_total             7433
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02375e2.cif
_cod_data_source_block           C2_trans_4
_cod_depositor_comments
'Adding full bibliography for 7157282--7157285.cif.'
_cod_database_code               7157285
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C32 H34 F12 N2 O8 S2'
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All S(H) groups
2. Uiso/Uaniso restraints and constraints
Uiso(F12B) = Uiso(F12A)
Uiso(F11A) = Uiso(F11B)
Uiso(F10B) = Uiso(F10A)
Uiso(F12C) = Uiso(F12B)
Uiso(F10C) = Uiso(F10B)
Uiso(F11C) = Uiso(F11B)
3. Others
 Sof(F10B)=Sof(F11B)=Sof(F12B)=0.75*(1-FVAR(2))
 Sof(F10A)=Sof(F11A)=Sof(F12A)=0.75*FVAR(2)
 Fixed Sof: F10C(0.25) F11C(0.25) F12C(0.25)
4.a Ternary CH refined with riding coordinates:
 C2(H2B), C3(H3), C9(H9), C10(H10)
4.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C11(H11A,
 H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B)
4.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), N2(H2A), C18(H18), C20(H20), C22(H22), C26(H26), C28(H28), C30(H30)
;
_shelx_res_checksum              73482
_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 1.342
_oxdiff_exptl_absorpt_empirical_full_min 0.785