S-Alkylation of Thiacalixarenes: How the Regio- and Stereoselectivities Depend on the Starting Conformation
Ondrej Kundrat; Hana Dvorakova; Stanislav Böhm; Vaclav Eigner; Pavel Lhotak; Journal of Organic Chemistry 77 (2012) 2272–2278; doi:10.1021/jo202571h

data_4027038
_publ_section_title
;
 S-Alkylation of Thiacalixarenes: How the Regio- and Stereoselectivities
 Depend on the Starting Conformation
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              2272
_journal_page_last               2278
_journal_paper_doi               10.1021/jo202571h
_journal_volume                  77
_journal_year                    2012
_chemical_formula_moiety         'C54 H78 O4 S4, 2(C F3 O3 S), C3 H6 O'
_chemical_formula_sum            'C59 H84 F6 O11 S6'
_chemical_formula_weight         1275.69
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_cell_angle_alpha                79.467(2)
_cell_angle_beta                 87.473(2)
_cell_angle_gamma                72.882(2)
_cell_formula_units_Z            2
_cell_length_a                   13.2733(4)
_cell_length_b                   13.6491(4)
_cell_length_c                   19.3858(4)
_cell_measurement_reflns_used    16896
_cell_measurement_temperature    170
_cell_measurement_theta_max      75
_cell_measurement_theta_min      4
_cell_volume                     3299.78(16)
_computing_cell_refinement       'CrysAlis RED, (Oxford Diffraction, 2002)'
_computing_data_collection       'Xcalibur, (Oxford Diffraction, 2002)'
_computing_data_reduction        'CrysAlis RED, (Oxford Diffraction, 2002)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_diffrn_ambient_pressure         101
_diffrn_ambient_temperature      170
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Oxford Diffraction XCALIBUR'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54180
_diffrn_reflns_av_R_equivalents  0.025
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24786
_diffrn_reflns_theta_full        68.468
_diffrn_reflns_theta_max         75.240
_diffrn_reflns_theta_min         4.167
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.516
_exptl_absorpt_correction_T_max  0.67
_exptl_absorpt_correction_T_min  0.48
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.284
_exptl_crystal_description       prism
_exptl_crystal_F_000             1352.000
_exptl_crystal_size_max          0.370
_exptl_crystal_size_mid          0.240
_exptl_crystal_size_min          0.160
_refine_diff_density_max         0.68
_refine_diff_density_min         -0.71
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.0153
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1000
_refine_ls_number_reflns         13136
_refine_ls_number_restraints     335
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0542
_refine_ls_shift/su_max          0.0077893
_refine_ls_shift/su_mean         0.0001135
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) 
 [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] 
 where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax 
 Method = Robust Weighting (Prince, 1982) 
 W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ 
 A~i~ are: 
 0.286E+04 0.486E+04 0.299E+04 0.124E+04 269. 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.1680
_refine_ls_wR_factor_gt          0.1610
_refine_ls_wR_factor_ref         0.1680
_reflns_limit_h_max              16
_reflns_limit_h_min              -15
_reflns_limit_k_max              17
_reflns_limit_k_min              -16
_reflns_limit_l_max              24
_reflns_limit_l_min              0
_reflns_number_gt                12156
_reflns_number_total             13136
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.83
_oxford_diffrn_Wilson_scale      0.12
_oxford_refine_ls_r_factor_ref   0.0570
_oxford_refine_ls_scale          3.27(3)
_oxford_reflns_number_all        13136
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_cod_data_source_file            jo202571h_si_001.cif
_cod_data_source_block           1
_cod_original_cell_volume        3299.77(16)
_cod_original_sg_symbol_H-M      'P -1 '
_cod_database_code               4027038
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
RIDE C   (   5,X'S) H   (  51,X'S) H   (  52,X'S) 
RIDE C   (   6,X'S) H   (  62,X'S) H   (  61,X'S) 
RIDE C   (   7,X'S) H   (  71,X'S) H   (  73,X'S) H   (  72,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) H   ( 132,X'S) 
RIDE C   (  14,X'S) H   ( 142,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) H   ( 153,X'S) H   ( 152,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) H   ( 212,X'S) 
RIDE C   (  22,X'S) H   ( 222,X'S) H   ( 221,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) H   ( 233,X'S) H   ( 232,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  35,X'S) H   ( 352,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) H   ( 362,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) H   ( 372,X'S) H   ( 373,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  40,X'S) H   ( 401,X'S) 
RIDE C   (  42,X'S) H   ( 423,X'S) H   ( 421,X'S) H   ( 422,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) 
RIDE C   (  47,X'S) H   ( 471,X'S) 
RIDE C   (  49,X'S) H   ( 491,X'S) 
RIDE C   (  51,X'S) H   ( 512,X'S) H   ( 513,X'S) H   ( 511,X'S) 
RIDE C   (  52,X'S) H   ( 521,X'S) H   ( 523,X'S) H   ( 522,X'S) 
RIDE C   (  53,X'S) H   ( 531,X'S) H   ( 532,X'S) H   ( 533,X'S) 
RIDE C   (  54,X'S) H   ( 542,X'S) H   ( 541,X'S) H   ( 543,X'S) 
RIDE C   ( 111,X'S) H   (1111,X'S) H   (1112,X'S) H   (1113,X'S) 
RIDE C   ( 112,X'S) H   (1121,X'S) H   (1122,X'S) H   (1123,X'S) 
RIDE C   ( 113,X'S) H   (1132,X'S) H   (1131,X'S) H   (1133,X'S) 
RIDE C   ( 211,X'S) H   (2111,X'S) H   (2112,X'S) H   (2113,X'S) 
RIDE C   ( 212,X'S) H   (2121,X'S) H   (2123,X'S) H   (2122,X'S) 
RIDE C   ( 213,X'S) H   (2132,X'S) H   (2133,X'S) H   (2131,X'S) 
RIDE C   ( 121,X'S) H   (1211,X'S) H   (1212,X'S) H   (1213,X'S) 
RIDE C   ( 122,X'S) H   (1221,X'S) H   (1222,X'S) H   (1223,X'S) 
RIDE C   ( 123,X'S) H   (1232,X'S) H   (1231,X'S) H   (1233,X'S) 
RIDE C   ( 221,X'S) H   (2212,X'S) H   (2211,X'S) H   (2213,X'S) 
RIDE C   ( 222,X'S) H   (2221,X'S) H   (2223,X'S) H   (2222,X'S) 
RIDE C   ( 223,X'S) H   (2232,X'S) H   (2231,X'S) H   (2233,X'S) 
RIDE C   ( 131,X'S) H   (1312,X'S) H   (1311,X'S) H   (1313,X'S) 
RIDE C   ( 132,X'S) H   (1321,X'S) H   (1322,X'S) H   (1323,X'S) 
RIDE C   ( 133,X'S) H   (1331,X'S) H   (1333,X'S) H   (1332,X'S) 
RIDE C   ( 231,X'S) H   (2312,X'S) H   (2313,X'S) H   (2311,X'S) 
RIDE C   ( 232,X'S) H   (2321,X'S) H   (2322,X'S) H   (2323,X'S) 
RIDE C   ( 233,X'S) H   (2332,X'S) H   (2331,X'S) H   (2333,X'S) 
RIDE C   ( 142,X'S) H   (1421,X'S) H   (1422,X'S) H   (1423,X'S) 
RIDE C   ( 143,X'S) H   (1431,X'S) H   (1433,X'S) H   (1432,X'S) 
RIDE C   ( 242,X'S) H   (2421,X'S) H   (2422,X'S) H   (2423,X'S) 
RIDE C   ( 243,X'S) H   (2433,X'S) H   (2432,X'S) H   (2431,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
DISTANCE 1.420000 , 0.020000 = S(100) TO O(101) 
DISTANCE 1.420000 , 0.020000 = S(100) TO O(102) 
DISTANCE 1.420000 , 0.020000 = S(100) TO O(103) 
DISTANCE 2.410000 , 0.020000 = O(101) TO O(102) 
DISTANCE 2.410000 , 0.020000 = O(102) TO O(103) 
DISTANCE 2.410000 , 0.020000 = O(103) TO O(101) 
DISTANCE 1.830000 , 0.020000 = S(100) TO C(104) 
DISTANCE 2.610000 , 0.020000 = S(100) TO F(105) 
DISTANCE 2.610000 , 0.020000 = S(100) TO F(106) 
DISTANCE 2.610000 , 0.020000 = S(100) TO F(107) 
DISTANCE 1.330000 , 0.020000 = C(104) TO F(105) 
DISTANCE 1.330000 , 0.020000 = C(104) TO F(106) 
DISTANCE 1.330000 , 0.020000 = C(104) TO F(107) 
DISTANCE 2.130000 , 0.020000 = F(105) TO F(106) 
DISTANCE 2.130000 , 0.020000 = F(106) TO F(107) 
DISTANCE 2.130000 , 0.020000 = F(107) TO F(105) 
DISTANCE 2.550000 , 0.020000 = C(104) TO O(101) 
DISTANCE 2.550000 , 0.020000 = C(104) TO O(102) 
DISTANCE 2.550000 , 0.020000 = C(104) TO O(103) 
DISTANCE 1.420000 , 0.020000 = S(200) TO O(201) 
DISTANCE 1.420000 , 0.020000 = S(200) TO O(202) 
DISTANCE 1.420000 , 0.020000 = S(200) TO O(203) 
DISTANCE 2.410000 , 0.020000 = O(201) TO O(202) 
DISTANCE 2.410000 , 0.020000 = O(202) TO O(203) 
DISTANCE 2.410000 , 0.020000 = O(203) TO O(201) 
DISTANCE 1.830000 , 0.020000 = S(200) TO C(204) 
DISTANCE 2.610000 , 0.020000 = S(200) TO F(205) 
DISTANCE 2.610000 , 0.020000 = S(200) TO F(206) 
DISTANCE 2.610000 , 0.020000 = S(200) TO F(207) 
DISTANCE 1.330000 , 0.020000 = C(204) TO F(205) 
DISTANCE 1.330000 , 0.020000 = C(204) TO F(206) 
DISTANCE 1.330000 , 0.020000 = C(204) TO F(207) 
DISTANCE 2.130000 , 0.020000 = F(205) TO F(206) 
DISTANCE 2.130000 , 0.020000 = F(206) TO F(207) 
DISTANCE 2.130000 , 0.020000 = F(207) TO F(205) 
DISTANCE 2.550000 , 0.020000 = C(204) TO O(201) 
DISTANCE 2.550000 , 0.020000 = C(204) TO O(202) 
DISTANCE 2.550000 , 0.020000 = C(204) TO O(203) 
DISTANCE 1.420000 , 0.020000 = S(300) TO O(301) 
DISTANCE 1.420000 , 0.020000 = S(300) TO O(302) 
DISTANCE 1.420000 , 0.020000 = S(300) TO O(303) 
DISTANCE 2.410000 , 0.020000 = O(301) TO O(302) 
DISTANCE 2.410000 , 0.020000 = O(302) TO O(303) 
DISTANCE 2.410000 , 0.020000 = O(303) TO O(301) 
DISTANCE 1.830000 , 0.020000 = S(300) TO C(304) 
DISTANCE 2.610000 , 0.020000 = S(300) TO F(305) 
DISTANCE 2.610000 , 0.020000 = S(300) TO F(306) 
DISTANCE 2.610000 , 0.020000 = S(300) TO F(307) 
DISTANCE 1.330000 , 0.020000 = C(304) TO F(305) 
DISTANCE 1.330000 , 0.020000 = C(304) TO F(306) 
DISTANCE 1.330000 , 0.020000 = C(304) TO F(307) 
DISTANCE 2.130000 , 0.020000 = F(305) TO F(306) 
DISTANCE 2.130000 , 0.020000 = F(306) TO F(307) 
DISTANCE 2.130000 , 0.020000 = F(307) TO F(305) 
DISTANCE 2.550000 , 0.020000 = C(204) TO O(201) 
DISTANCE 2.550000 , 0.020000 = C(204) TO O(202) 
DISTANCE 2.550000 , 0.020000 = C(204) TO O(203) 
U(IJ)'S  0.0, 0.001000 = S(100) TO S(200) 
U(IJ)'S  0.0, 0.002000 = O(101) TO O(201) 
U(IJ)'S  0.0, 0.002000 = O(102) TO O(202) 
U(IJ)'S  0.0, 0.002000 = O(103) TO O(203) 
U(IJ)'S  0.0, 0.010000 = C(104) TO C(204) 
U(IJ)'S  0.0, 0.020000 = F(105) TO F(205) 
U(IJ)'S  0.0, 0.020000 = F(106) TO F(206) 
U(IJ)'S  0.0, 0.020000 = F(107) TO F(207) 
U(IJ)'S  0.0, 0.040000 = S(100) TO O(101) 
U(IJ)'S  0.0, 0.040000 = S(100) TO O(102) 
U(IJ)'S  0.0, 0.040000 = S(100) TO O(103) 
U(IJ)'S  0.0, 0.040000 = S(200) TO O(201) 
U(IJ)'S  0.0, 0.040000 = S(200) TO O(202) 
U(IJ)'S  0.0, 0.040000 = S(200) TO O(203) 
U(IJ)'S  0.0, 0.001000 = S(100) TO S(300) 
U(IJ)'S  0.0, 0.002000 = O(101) TO O(301) 
U(IJ)'S  0.0, 0.002000 = O(102) TO O(302) 
U(IJ)'S  0.0, 0.002000 = O(103) TO O(303) 
U(IJ)'S  0.0, 0.010000 = C(104) TO C(304) 
U(IJ)'S  0.0, 0.020000 = F(105) TO F(305) 
U(IJ)'S  0.0, 0.020000 = F(106) TO F(306) 
U(IJ)'S  0.0, 0.020000 = F(107) TO F(307) 
DISTANCE 1.540000 , 0.050000 = C(110) TO C(111) 
DISTANCE 1.540000 , 0.050000 = C(110) TO C(112) 
DISTANCE 1.540000 , 0.050000 = C(110) TO C(113) 
DISTANCE 2.340000 , 0.050000 = C(111) TO C(112) 
DISTANCE 2.340000 , 0.050000 = C(112) TO C(113) 
DISTANCE 2.340000 , 0.050000 = C(113) TO C(111) 
DISTANCE 1.540000 , 0.050000 = C(110) TO C(211) 
DISTANCE 1.540000 , 0.050000 = C(110) TO C(212) 
DISTANCE 1.540000 , 0.050000 = C(110) TO C(213) 
DISTANCE 2.340000 , 0.050000 = C(211) TO C(212) 
DISTANCE 2.340000 , 0.050000 = C(212) TO C(213) 
DISTANCE 2.340000 , 0.050000 = C(213) TO C(211) 
U(IJ)'S  0.0, 0.010000 = C(111) TO C(211) 
U(IJ)'S  0.0, 0.010000 = C(112) TO C(212) 
U(IJ)'S  0.0, 0.010000 = C(113) TO C(213) 
DISTANCE 1.540000 , 0.050000 = C(120) TO C(121) 
DISTANCE 1.540000 , 0.050000 = C(120) TO C(122) 
DISTANCE 1.540000 , 0.050000 = C(120) TO C(123) 
DISTANCE 2.340000 , 0.050000 = C(121) TO C(122) 
DISTANCE 2.340000 , 0.050000 = C(122) TO C(123) 
DISTANCE 2.340000 , 0.050000 = C(123) TO C(121) 
DISTANCE 1.540000 , 0.050000 = C(120) TO C(221) 
DISTANCE 1.540000 , 0.050000 = C(120) TO C(222) 
DISTANCE 1.540000 , 0.050000 = C(120) TO C(223) 
DISTANCE 2.340000 , 0.020000 = C(221) TO C(222) 
DISTANCE 2.340000 , 0.020000 = C(222) TO C(223) 
DISTANCE 2.340000 , 0.020000 = C(223) TO C(221) 
U(IJ)'S  0.0, 0.010000 = C(121) TO C(221) 
U(IJ)'S  0.0, 0.010000 = C(122) TO C(222) 
U(IJ)'S  0.0, 0.010000 = C(123) TO C(223) 
DISTANCE 1.540000 , 0.050000 = C(130) TO C(131) 
DISTANCE 1.540000 , 0.050000 = C(130) TO C(132) 
DISTANCE 1.540000 , 0.050000 = C(130) TO C(133) 
DISTANCE 2.340000 , 0.050000 = C(131) TO C(132) 
DISTANCE 2.340000 , 0.050000 = C(132) TO C(133) 
DISTANCE 2.340000 , 0.050000 = C(133) TO C(131) 
DISTANCE 1.540000 , 0.050000 = C(130) TO C(231) 
DISTANCE 1.540000 , 0.050000 = C(130) TO C(232) 
DISTANCE 1.540000 , 0.050000 = C(130) TO C(233) 
DISTANCE 2.340000 , 0.020000 = C(231) TO C(232) 
DISTANCE 2.340000 , 0.020000 = C(232) TO C(233) 
DISTANCE 2.340000 , 0.020000 = C(233) TO C(231) 
U(IJ)'S  0.0, 0.010000 = C(131) TO C(233) 
U(IJ)'S  0.0, 0.010000 = C(132) TO C(231) 
U(IJ)'S  0.0, 0.010000 = C(133) TO C(232) 
U(IJ)'S  0.0, 0.010000 = C(130) TO C(131) 
DISTANCE 1.200000 , 0.050000 = O(140) TO C(141) 
DISTANCE 1.340000 , 0.050000 = C(141) TO C(142) 
DISTANCE 1.340000 , 0.050000 = C(141) TO C(143) 
ANGLE 120.000000 , 1.000000 = O(140) TO C(141) TO C(142) 
ANGLE 120.000000 , 1.000000 = O(140) TO C(141) TO C(143) 
ANGLE 120.000000 , 1.000000 = C(142) TO C(141) TO C(143) 
PLANAR 0.010000  O(140) C(141) C(142) C(143) 
DISTANCE 1.200000 , 0.050000 = O(240) TO C(241) 
DISTANCE 1.340000 , 0.050000 = C(241) TO C(242) 
DISTANCE 1.340000 , 0.050000 = C(241) TO C(243) 
ANGLE 120.000000 , 1.000000 = O(240) TO C(241) TO C(242) 
ANGLE 120.000000 , 1.000000 = O(240) TO C(241) TO C(243) 
ANGLE 120.000000 , 1.000000 = C(242) TO C(241) TO C(243) 
PLANAR 0.010000  O(240) C(241) C(242) C(243) 
U(IJ)'S  0.0, 0.010000 = O(140) TO O(240) 
U(IJ)'S  0.0, 0.010000 = C(141) TO C(241) 
U(IJ)'S  0.0, 0.010000 = C(142) TO C(242) 
U(IJ)'S  0.0, 0.010000 = C(143) TO C(243) 
U(IJ)'S  0.0, 0.010000 = C(59) TO F(61) 
END                                                                             
;