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_7157282
_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      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-16
_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                90
_cell_angle_beta                 121.245(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.2004(5)
_cell_length_b                   12.6594(2)
_cell_length_c                   19.4388(5)
_cell_measurement_reflns_used    4064
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      73.5800
_cell_measurement_theta_min      4.3770
_cell_volume                     3829.2(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 0.999
_diffrn_measured_fraction_theta_max 0.974
_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     34.00 113.00   1.00    8.00    --  110.40-111.00  30.00   79
  2  \w     68.00 131.00   1.00    8.00    --  110.40 -77.00  30.00   63
  3  \w     81.00 167.00   1.00    8.00    --  110.40  45.00  60.00   86
  4  \w    104.00 167.00   1.00    8.00    --  110.40 111.00   0.00   63
  5  \w    106.00 169.00   1.00    8.00    --  110.40  61.00 120.00   63
  6  \w     80.00 178.00   1.00    8.00    --  110.40  77.00  90.00   98
  7  \w     66.00 103.00   1.00    2.00    --   37.56 178.00 120.00   37
  8  \w   -115.00  -6.00   1.00    2.00    --  -37.56 -57.00  60.00  109
  9  \w   -115.00  -8.00   1.00    2.00    --  -37.56 -57.00-180.00  107
;
_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      0.0416272000
_diffrn_orient_matrix_UB_12      -0.0317370000
_diffrn_orient_matrix_UB_13      -0.0486990000
_diffrn_orient_matrix_UB_21      -0.0589408000
_diffrn_orient_matrix_UB_22      -0.0975302000
_diffrn_orient_matrix_UB_23      -0.0323584000
_diffrn_orient_matrix_UB_31      -0.0678032000
_diffrn_orient_matrix_UB_32      0.0654125000
_diffrn_orient_matrix_UB_33      -0.0719261000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0128
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            6955
_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         73.513
_diffrn_reflns_theta_min         4.417
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.256
_exptl_absorpt_correction_T_max  0.730
_exptl_absorpt_correction_T_min  0.597
_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    1.503
_exptl_crystal_description       prism
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.306
_exptl_crystal_size_mid          0.253
_exptl_crystal_size_min          0.197
_refine_diff_density_max         0.678
_refine_diff_density_min         -0.472
_refine_diff_density_rms         0.058
_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     310
_refine_ls_number_reflns         3759
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0630
_refine_ls_R_factor_gt           0.0584
_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^)+(0.1250P)^2^+2.5050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1835
_refine_ls_wR_factor_ref         0.1915
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3328
_reflns_number_total             3759
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02375e2.cif
_cod_data_source_block           C2_cis_4
_cod_depositor_comments
'Adding full bibliography for 7157282--7157285.cif.'
_cod_original_cell_volume        3829.20(19)
_cod_database_code               7157282
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C32 H34 F12 N2 O8 S2'
_reflns_odcompleteness_completeness 99.83
_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
F4A \\sim F4B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F5A \\sim F5B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F6A \\sim F6B: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F1B \\sim F1A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F2B \\sim F2A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
F3B \\sim F3A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
3. Others
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(1)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C4(H4), C6(H6)
4.b Secondary CH2 refined with riding coordinates:
 C1(H1B,H1C), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C7(H7A,H7B)
4.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), C10(H10), C12(H12), C14(H14)
4.d Idealised tetrahedral OH refined as rotating group:
 S1(H1)
;
_shelx_res_checksum              24934
_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 1.274
_oxdiff_exptl_absorpt_empirical_full_min 0.782