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_7157284
_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         'C36 H38 F12 N2 O10 S2'
_chemical_formula_sum            'C36 H38 F12 N2 O10 S2'
_chemical_formula_weight         950.80
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-15
_audit_creation_method           SHELXL-2013
_audit_update_record
;
2019-09-09 deposited with the CCDC.	2019-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.432(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6208(2)
_cell_length_b                   17.3037(4)
_cell_length_c                   25.0189(4)
_cell_measurement_reflns_used    6258
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      73.4820
_cell_measurement_theta_min      4.3420
_cell_volume                     4152.58(15)
_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    'ShelXL (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 1.000
_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     74.00 109.00   1.00   50.00    --  110.40 -94.00   0.00   35
  2  \w     46.00 110.00   1.00   50.00    --  110.40-111.00 -30.00   64
  3  \w     26.00 136.00   1.00   50.00    --  110.40 -77.00 150.00  110
  4  \w     97.00 177.00   1.00   50.00    --  110.40  30.00  60.00   80
  5  \w    106.00 172.00   1.00   50.00    --  110.40 111.00 120.00   66
  6  \w     91.00 122.00   1.00   12.50    --   37.69 178.00 -60.00   31
  7  \w     72.00 120.00   1.00   12.50    --   37.69 178.00  30.00   48
  8  \w    115.00 154.00   1.00   50.00    --  110.40  92.00-117.00   39
  9  \w    110.00 136.00   1.00   50.00    --  110.40 178.00-120.00   26
 10  \w     61.00 130.00   1.00   12.50    --   37.69 178.00-180.00   69
 11  \w     77.00 153.00   1.00   50.00    --  110.40  61.00 120.00   76
 12  \w   -114.00  -4.00   1.00   12.50    --  -37.69 -19.00 -90.00  110
;
_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      -0.0352695000
_diffrn_orient_matrix_UB_12      -0.0814908000
_diffrn_orient_matrix_UB_13      0.0197770000
_diffrn_orient_matrix_UB_21      -0.1097473000
_diffrn_orient_matrix_UB_22      -0.0091834000
_diffrn_orient_matrix_UB_23      -0.0477561000
_diffrn_orient_matrix_UB_31      0.1117967000
_diffrn_orient_matrix_UB_32      -0.0346670000
_diffrn_orient_matrix_UB_33      -0.0338145000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            16134
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         73.594
_diffrn_reflns_theta_min         3.108
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.173
_exptl_absorpt_correction_T_max  0.949
_exptl_absorpt_correction_T_min  0.629
_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    1.521
_exptl_crystal_description       needle
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.445
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.029
_refine_diff_density_max         1.539
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     563
_refine_ls_number_reflns         8157
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.1096
_refine_ls_R_factor_gt           0.0883
_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^)+(0.1190P)^2^+9.2120P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2357
_refine_ls_wR_factor_ref         0.2567
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6218
_reflns_number_total             8157
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02375e2.cif
_cod_data_source_block           C2_trans_3a
_cod_depositor_comments
'Adding full bibliography for 7157282--7157285.cif.'
_cod_database_code               7157284
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C36 H38 F12 N2 O10 S2'
_reflns_odcompleteness_completeness 99.94
_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
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 O43A-C41A
 1.2 with sigma of 0.02
 O43B-C41B
 1.2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S2A) = Uanis(S2B)
Uanis(O43A) = Uanis(O43B)
Uanis(C41A) = Uanis(C41B)
Uanis(C20A) = Uanis(C20B)
Uiso(F36B) = Uiso(F36A)
Uiso(F37B) = Uiso(F37A)
Uiso(F35B) = Uiso(F35A)
Uiso(F31B) = Uiso(F31A)
Uiso(F33B) = Uiso(F33A)
Uiso(F32A) = Uiso(F32B)
4. Others
 Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C20B)=Sof(H20C)=Sof(H20D)=Sof(S2B)=
 Sof(C41B)=Sof(O43B)=Sof(H11A)=1-FVAR(1)
 Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(S2A)=Sof(C41A)=Sof(O43A)=Sof(H42A)=
 Sof(H42B)=Sof(H42C)=Sof(H11)=FVAR(1)
 Sof(F35B)=Sof(F36B)=Sof(F37B)=1-FVAR(2)
 Sof(F35A)=Sof(F36A)=Sof(F37A)=FVAR(2)
 Sof(F31B)=Sof(F32B)=Sof(F33B)=1-FVAR(3)
 Sof(F31A)=Sof(F32A)=Sof(F33A)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C11(H11), C11(H11A), C12(H12)
5.b Secondary CH2 refined with riding coordinates:
 C20A(H20A,H20B), C20B(H20C,H20D), C1(H1A,H1B), C5(H5A,H5B), C6(H6A,H6B),
 C8(H8A,H8B), C9(H9A,H9B), C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B),
 C18(H18A,H18B)
5.c Me refined with riding coordinates:
 C42(H42A,H42B,H42C), C42(H42D,H42E,H42F)
5.d Aromatic/amide H refined with riding coordinates:
 N23(H23), N46(H46), C25(H25), C27(H27), C29(H29), C48(H48), C50(H50), C52(H52)
5.e Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C)
;
_shelx_res_checksum              51711
_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 1.566
_oxdiff_exptl_absorpt_empirical_full_min 0.424