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_7157283
_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 H42 F12 N2 O8 S2'
_chemical_formula_sum            'C36 H42 F12 N2 O8 S2'
_chemical_formula_weight         922.83
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-10-11
_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                 97.5197(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.68201(13)
_cell_length_b                   18.7358(3)
_cell_length_c                   25.4056(4)
_cell_measurement_reflns_used    12281
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      73.2830
_cell_measurement_theta_min      3.4830
_cell_volume                     4097.05(11)
_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
_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 0.988
_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     21.00 110.00   1.00    2.00    --   37.69  57.00 -30.00   89
  2  \w     91.00 116.00   1.00    2.00    --   37.69  57.00-150.00   25
  3  \w     88.00 168.00   1.00    8.00    --  110.40  30.00-120.00   80
  4  \w    100.00 146.00   1.00    8.00    --  110.40  45.00 -30.00   46
  5  \w    117.00 174.00   1.00    8.00    --  110.40  61.00  30.00   57
  6  \w     99.00 127.00   1.00    2.00    --   37.69 178.00 -60.00   28
  7  \w     80.00 161.00   1.00    8.00    --  110.40  61.00   0.00   81
  8  \w     85.00 130.00   1.00    2.00    --   37.69 178.00 150.00   45
  9  \w     28.00  55.00   1.00    2.00    --   37.69  57.00-150.00   27
 10  \w     90.00 177.00   1.00    8.00    --  110.40  45.00-180.00   87
 11  \w     90.00 115.00   1.00    8.00    --  110.40-111.00-180.00   25
 12  \w     54.00 109.00   1.00    8.00    --  110.40 -94.00 -60.00   55
 13  \w     42.00 109.00   1.00    8.00    --  110.40 -94.00  30.00   67
 14  \w     56.00 145.00   1.00    8.00    --  110.40 -77.00  90.00   89
 15  \w     47.00 134.00   1.00    8.00    --  110.40 -45.00   0.00   87
 16  \w     37.00 112.00   1.00    8.00    --  110.40-111.00 -90.00   75
 17  \w     32.00 132.00   1.00    8.00    --  110.40 -45.00-120.00  100
 18  \w    -67.00  40.00   1.00    2.00    --  -37.69  38.00  90.00  107
 19  \w    -72.00  41.00   1.00    2.00    --  -37.69  65.00 -37.00  113
 20  \w   -107.00 -48.00   1.00    2.00    --  -37.69 -57.00  30.00   59
;
_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      0.0124479000
_diffrn_orient_matrix_UB_12      0.0801355000
_diffrn_orient_matrix_UB_13      -0.0123178000
_diffrn_orient_matrix_UB_21      0.0995351000
_diffrn_orient_matrix_UB_22      -0.0176334000
_diffrn_orient_matrix_UB_23      -0.0442345000
_diffrn_orient_matrix_UB_31      -0.1482858000
_diffrn_orient_matrix_UB_32      -0.0051200000
_diffrn_orient_matrix_UB_33      -0.0404000000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0258
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            28125
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         73.633
_diffrn_reflns_theta_min         2.940
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.144
_exptl_absorpt_correction_T_max  0.863
_exptl_absorpt_correction_T_min  0.631
_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    1.496
_exptl_crystal_description       prism
_exptl_crystal_F_000             1904
_exptl_crystal_size_max          0.258
_exptl_crystal_size_mid          0.173
_exptl_crystal_size_min          0.075
_refine_diff_density_max         1.250
_refine_diff_density_min         -0.926
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     551
_refine_ls_number_reflns         8173
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0860
_refine_ls_R_factor_gt           0.0757
_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^)+(0.1020P)^2^+6.9280P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2015
_refine_ls_wR_factor_ref         0.2133
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6903
_reflns_number_total             8173
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02375e2.cif
_cod_data_source_block           C2_cis_3b
_cod_depositor_comments
'Adding full bibliography for 7157282--7157285.cif.'
_cod_database_code               7157283
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C36 H42 F12 N2 O8 S2'
_reflns_odcompleteness_completeness 99.96
_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
2. Uiso/Uaniso restraints and constraints
Uanis(F46A) = Uanis(F46B)
Uiso(F47A) = Uiso(F47B)
Uanis(F48A) = Uanis(F48B)
Uiso(F35B) = Uiso(F35A) = Uiso(F35C)
Uiso(F33B) = Uiso(F33A) = Uiso(F33C)
Uiso(F34B) = Uiso(F34A) = Uiso(F34C)
3. Others
 Sof(F46B)=Sof(F47B)=Sof(F48B)=1-FVAR(1)
 Sof(F46A)=Sof(F47A)=Sof(F48A)=FVAR(1)
 Fixed Sof: F33A(0.33333) F34A(0.33333) F35A(0.33333) F33B(0.33333)
 F34B(0.33333) F35B(0.33333) F33C(0.33333) F34C(0.33333) F35C(0.33333)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C9(H9), C10(H10), C18(H18)
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C12(H12A,H12B), C13(H13A,
 H13B), C15(H15A,H15B), C16(H16A,H16B), C53(H53A,H53B), C55(H55A,H55B),
 C57(H57A,H57B), C59(H59A,H59B)
4.c Aromatic/amide H refined with riding coordinates:
 N21(H21), N38(H38), C23(H23), C25(H25), C27(H27), C40(H40), C42(H42), C44(H44)
4.d Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C60(H60A,H60B,H60C)
;
_shelx_res_checksum              58779
_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 1.293
_oxdiff_exptl_absorpt_empirical_full_min 0.755