Aryl Methyl Sulfides as Substrates for Rhodium-Catalyzed Alkyne Carbothiolation: Arene Functionalization with Activating Group Recycling
Joel F. Hooper; Adrian B. Chaplin; Carlos González-Rodríguez; Amber L. Thompson; Andrew S. Weller; Michael C. Willis; Journal of the American Chemical Society 134 (2012) 2906–2909; doi:10.1021/ja2108992

data_4117461
_publ_contact_author             'Michael C. Willis & Andrew S. Weller'
_publ_contact_author_email
'michael.willis@chem.ox.ac.uk & andrew.weller@chem.ox.ac.uk'
_publ_section_title
;
 Aryl Methyl Sulfides as Substrates for Rhodium-Catalyzed Alkyne
 Carbothiolation: Arene Functionalization with Activating Group Recycling
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2906
_journal_page_last               2909
_journal_paper_doi               10.1021/ja2108992
_journal_volume                  134
_journal_year                    2012
_chemical_formula_moiety         'C45 H38 O2 P2 Rh S, C32 H12 B F24'
_chemical_formula_sum            'C77 H50 B F24 O2 P2 Rh S'
_chemical_formula_weight         1670.92
_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   difmap
_atom_sites_solution_primary     direct
_audit_creation_date             11-09-04
_audit_creation_method           CRYSTALS_ver_14.23
_cell_angle_alpha                117.813(4)
_cell_angle_beta                 91.160(3)
_cell_angle_gamma                102.919(3)
_cell_formula_units_Z            2
_cell_length_a                   11.6512(3)
_cell_length_b                   18.6314(6)
_cell_length_c                   19.4202(8)
_cell_measurement_reflns_used    14209
_cell_measurement_temperature    150
_cell_measurement_theta_max      32
_cell_measurement_theta_min      2
_cell_volume                     3596.2(3)
_computing_cell_refinement       'CrysAlis, (Oxford Diffraction, 2002)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2009)'
_computing_data_reduction        'CrysAlis, (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    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.882
_diffrn_measurement_device       area
_diffrn_measurement_device_details
;
CrystalLogic Kappa (3 circle)
;
_diffrn_measurement_device_type  'Rigaku Saturn724+'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  Synchrotron
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.68890
_diffrn_reflns_av_R_equivalents  0.153
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            81422
_diffrn_reflns_theta_full        25.122
_diffrn_reflns_theta_max         32.207
_diffrn_reflns_theta_min         1.757
_diffrn_source                   Synchrotron
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.421
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.71
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlis, (Oxford Diffraction, 2002)'
_exptl_crystal_colour            clear_pale_yellow
_exptl_crystal_density_diffrn    1.543
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_exptl_crystal_size_max          0.010
_exptl_crystal_size_mid          0.010
_exptl_crystal_size_min          0.005
_refine_diff_density_max         2.89
_refine_diff_density_min         -2.07
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.9382
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1113
_refine_ls_number_reflns         15112
_refine_ls_number_restraints     1140
_refine_ls_R_factor_all          0.0966
_refine_ls_R_factor_gt           0.0804
_refine_ls_shift/su_max          0.0059516
_refine_ls_shift/su_mean         0.0001461
_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: 
 0.440E+04 0.735E+04 0.467E+04 0.206E+04 505. 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.2405
_refine_ls_wR_factor_gt          0.2160
_refine_ls_wR_factor_ref         0.2405
_reflns_limit_h_max              17
_reflns_limit_h_min              -17
_reflns_limit_k_max              25
_reflns_limit_k_min              -28
_reflns_limit_l_max              29
_reflns_limit_l_min              0
_reflns_number_gt                11916
_reflns_number_total             24610
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.12
_oxford_diffrn_Wilson_scale      0.15
_oxford_refine_ls_r_factor_ref   0.0966
_oxford_refine_ls_scale          2.92(3)
_oxford_reflns_number_all        15112
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_oxford_structure_analysis_title DIA0137
_cod_data_source_file            ja2108992_si_002_3.cif
_cod_data_source_block           F
_cod_depositor_comments
;
The following automatic conversions were performed:

data name '_diffrn_measurement_device-type' was replaced with
'_diffrn_measurement_device_type' as specified in the replacement
file 'data/replacement-values/replacement_tags.lst'.

Automatic conversion script
Id: cif_correct_tags 9268 2022-04-12 08:56:07Z antanas 
;
_cod_original_sg_symbol_H-M      'P -1 '
_cod_database_code               4117461
_iucr_refine_instruction_details_constraints
;
BLOCK SCALE X'S, U'S 
EQUIV PART(1001,OCC) PART(1002,OCC) 
WEIGHT -1 PART(1002,OCC) 
EQUIV PART(2001,OCC) PART(2002,OCC) 
WEIGHT -1 PART(2002,OCC) 
EQUIV PART(3001,OCC) PART(3002,OCC) 
WEIGHT -1 PART(3002,OCC) 
EQUIV PART(4001,OCC) PART(4002,OCC) 
WEIGHT -1 PART(4002,OCC) 
EQUIV PART(5001,OCC) PART(5002,OCC) 
WEIGHT -1 PART(5002,OCC) 
RIDE C   (   3,X'S) H   (  31,X'S) 
RIDE C   (   4,X'S) H   (  41,X'S) 
RIDE C   (   5,X'S) H   (  51,X'S) 
RIDE C   (   6,X'S) H   (  61,X'S) 
RIDE C   (   8,X'S) H   (  82,X'S) H   (  81,X'S) H   (  83,X'S) 
RIDE C   (   9,X'S) H   (  92,X'S) H   (  91,X'S) H   (  93,X'S) 
RIDE C   (  12,X'S) H   ( 121,X'S) 
RIDE C   (  13,X'S) H   ( 131,X'S) 
RIDE C   (  14,X'S) H   ( 141,X'S) 
RIDE C   (  15,X'S) H   ( 151,X'S) 
RIDE C   (  18,X'S) H   ( 181,X'S) 
RIDE C   (  19,X'S) H   ( 191,X'S) 
RIDE C   (  20,X'S) H   ( 201,X'S) 
RIDE C   (  21,X'S) H   ( 211,X'S) 
RIDE C   (  23,X'S) H   ( 231,X'S) 
RIDE C   (  24,X'S) H   ( 241,X'S) 
RIDE C   (  25,X'S) H   ( 251,X'S) 
RIDE C   (  26,X'S) H   ( 261,X'S) 
RIDE C   (  27,X'S) H   ( 271,X'S) 
RIDE C   (  29,X'S) H   ( 291,X'S) 
RIDE C   (  30,X'S) H   ( 301,X'S) 
RIDE C   (  31,X'S) H   ( 311,X'S) 
RIDE C   (  32,X'S) H   ( 321,X'S) 
RIDE C   (  33,X'S) H   ( 331,X'S) 
RIDE C   (  35,X'S) H   ( 351,X'S) 
RIDE C   (  36,X'S) H   ( 361,X'S) 
RIDE C   (  37,X'S) H   ( 371,X'S) 
RIDE C   (  38,X'S) H   ( 381,X'S) 
RIDE C   (  39,X'S) H   ( 391,X'S) 
RIDE C   (  41,X'S) H   ( 411,X'S) 
RIDE C   (  42,X'S) H   ( 421,X'S) 
RIDE C   (  43,X'S) H   ( 431,X'S) 
RIDE C   (  44,X'S) H   ( 441,X'S) 
RIDE C   (  45,X'S) H   ( 451,X'S) 
RIDE C   ( 202,X'S) H   (2021,X'S) 
RIDE C   ( 204,X'S) H   (2041,X'S) 
RIDE C   ( 206,X'S) H   (2061,X'S) 
RIDE C   ( 212,X'S) H   (2121,X'S) 
RIDE C   ( 214,X'S) H   (2141,X'S) 
RIDE C   ( 216,X'S) H   (2161,X'S) 
RIDE C   ( 222,X'S) H   (2221,X'S) 
RIDE C   ( 224,X'S) H   (2241,X'S) 
RIDE C   ( 226,X'S) H   (2261,X'S) 
RIDE C   ( 232,X'S) H   (2321,X'S) 
RIDE C   ( 234,X'S) H   (2341,X'S) 
RIDE C   ( 236,X'S) H   (2361,X'S) 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
SAME  C(203)  C(207)  F(201)  F(202)  F(203)  AND 
CONT  C(203)  C(207)  F(203)  F(201)  F(202)  AND 
CONT  C(203)  C(207)  F(202)  F(203)  F(201)  AND 
CONT  C(203)  C(207)  F(301)  F(302)  F(303)  AND 
CONT  C(203)  C(207)  F(303)  F(301)  F(302)  AND 
CONT  C(203)  C(207)  F(302)  F(303)  F(301)  AND 
CONT  C(205)  C(208)  F(204)  F(205)  F(206)  AND 
CONT  C(205)  C(208)  F(206)  F(204)  F(205)  AND 
CONT  C(205)  C(208)  F(205)  F(206)  F(204)  AND 
CONT  C(205)  C(208)  F(304)  F(305)  F(306)  AND 
CONT  C(205)  C(208)  F(306)  F(304)  F(305)  AND 
CONT  C(205)  C(208)  F(305)  F(306)  F(304)  AND 
CONT  C(213)  C(217)  F(207)  F(208)  F(209)  AND 
CONT  C(213)  C(217)  F(209)  F(207)  F(208)  AND 
CONT  C(213)  C(217)  F(208)  F(209)  F(207)  AND 
CONT  C(213)  C(217)  F(307)  F(308)  F(309)  AND 
CONT  C(213)  C(217)  F(309)  F(307)  F(308)  AND 
CONT  C(213)  C(217)  F(308)  F(309)  F(307)  AND 
CONT  C(233)  C(237)  F(219)  F(220)  F(221)  AND 
CONT  C(233)  C(237)  F(221)  F(219)  F(220)  AND 
CONT  C(233)  C(237)  F(220)  F(221)  F(219)  AND 
CONT  C(233)  C(237)  F(319)  F(320)  F(321)  AND 
CONT  C(233)  C(237)  F(321)  F(319)  F(320)  AND 
CONT  C(233)  C(237)  F(320)  F(321)  F(319)  AND 
CONT  C(235)  C(238)  F(222)  F(223)  F(224)  AND 
CONT  C(235)  C(238)  F(224)  F(222)  F(223)  AND 
CONT  C(235)  C(238)  F(223)  F(224)  F(222)  AND 
CONT  C(235)  C(238)  F(322)  F(323)  F(324)  AND 
CONT  C(235)  C(238)  F(324)  F(322)  F(323)  AND 
CONT  C(235)  C(238)  F(323)  F(324)  F(322) 
DELU  0.01    C(203)  C(207)  F(201)  F(202)  F(203)  AND 
CONT  C(203)  C(207)  F(203)  F(201)  F(202)  AND 
CONT  C(203)  C(207)  F(202)  F(203)  F(201)  AND 
CONT  C(203)  C(207)  F(301)  F(302)  F(303)  AND 
CONT  C(203)  C(207)  F(303)  F(301)  F(302)  AND 
CONT  C(203)  C(207)  F(302)  F(303)  F(301)  AND 
CONT  C(205)  C(208)  F(204)  F(205)  F(206)  AND 
CONT  C(205)  C(208)  F(206)  F(204)  F(205)  AND 
CONT  C(205)  C(208)  F(205)  F(206)  F(204)  AND 
CONT  C(205)  C(208)  F(304)  F(305)  F(306)  AND 
CONT  C(205)  C(208)  F(306)  F(304)  F(305)  AND 
CONT  C(205)  C(208)  F(305)  F(306)  F(304)  AND 
CONT  C(213)  C(217)  F(207)  F(208)  F(209)  AND 
CONT  C(213)  C(217)  F(209)  F(207)  F(208)  AND 
CONT  C(213)  C(217)  F(208)  F(209)  F(207)  AND 
CONT  C(213)  C(217)  F(307)  F(308)  F(309)  AND 
CONT  C(213)  C(217)  F(309)  F(307)  F(308)  AND 
CONT  C(213)  C(217)  F(308)  F(309)  F(307)  AND 
CONT  C(233)  C(237)  F(219)  F(220)  F(221)  AND 
CONT  C(233)  C(237)  F(221)  F(219)  F(220)  AND 
CONT  C(233)  C(237)  F(220)  F(221)  F(219)  AND 
CONT  C(233)  C(237)  F(319)  F(320)  F(321)  AND 
CONT  C(233)  C(237)  F(321)  F(319)  F(320)  AND 
CONT  C(233)  C(237)  F(320)  F(321)  F(319)  AND 
CONT  C(235)  C(238)  F(222)  F(223)  F(224)  AND 
CONT  C(235)  C(238)  F(224)  F(222)  F(223)  AND 
CONT  C(235)  C(238)  F(223)  F(224)  F(222)  AND 
CONT  C(235)  C(238)  F(322)  F(323)  F(324)  AND 
CONT  C(235)  C(238)  F(324)  F(322)  F(323)  AND 
CONT  C(235)  C(238)  F(323)  F(324)  F(322) 
SIMU  0.01    C(203)  C(207)  F(201)  F(202)  F(203)  AND 
CONT  C(203)  C(207)  F(203)  F(201)  F(202)  AND 
CONT  C(203)  C(207)  F(202)  F(203)  F(201)  AND 
CONT  C(203)  C(207)  F(301)  F(302)  F(303)  AND 
CONT  C(203)  C(207)  F(303)  F(301)  F(302)  AND 
CONT  C(203)  C(207)  F(302)  F(303)  F(301)  AND 
CONT  C(205)  C(208)  F(204)  F(205)  F(206)  AND 
CONT  C(205)  C(208)  F(206)  F(204)  F(205)  AND 
CONT  C(205)  C(208)  F(205)  F(206)  F(204)  AND 
CONT  C(205)  C(208)  F(304)  F(305)  F(306)  AND 
CONT  C(205)  C(208)  F(306)  F(304)  F(305)  AND 
CONT  C(205)  C(208)  F(305)  F(306)  F(304)  AND 
CONT  C(213)  C(217)  F(207)  F(208)  F(209)  AND 
CONT  C(213)  C(217)  F(209)  F(207)  F(208)  AND 
CONT  C(213)  C(217)  F(208)  F(209)  F(207)  AND 
CONT  C(213)  C(217)  F(307)  F(308)  F(309)  AND 
CONT  C(213)  C(217)  F(309)  F(307)  F(308)  AND 
CONT  C(213)  C(217)  F(308)  F(309)  F(307)  AND 
CONT  C(233)  C(237)  F(219)  F(220)  F(221)  AND 
CONT  C(233)  C(237)  F(221)  F(219)  F(220)  AND 
CONT  C(233)  C(237)  F(220)  F(221)  F(219)  AND 
CONT  C(233)  C(237)  F(319)  F(320)  F(321)  AND 
CONT  C(233)  C(237)  F(321)  F(319)  F(320)  AND 
CONT  C(233)  C(237)  F(320)  F(321)  F(319)  AND 
CONT  C(235)  C(238)  F(222)  F(223)  F(224)  AND 
CONT  C(235)  C(238)  F(224)  F(222)  F(223)  AND 
CONT  C(235)  C(238)  F(223)  F(224)  F(222)  AND 
CONT  C(235)  C(238)  F(322)  F(323)  F(324)  AND 
CONT  C(235)  C(238)  F(324)  F(322)  F(323)  AND 
CONT  C(235)  C(238)  F(323)  F(324)  F(322) 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;