Palladium-Catalyzed Synthesis of α-Carbonyl-α'-(Hetero)aryl Sulfoxonium Ylides: Scope and Insight into the Mechanism.
Janot, Christopher; Chagnoleau, Jean-Baptiste; Halcovitch, Nathan R.; Muir, James C.; Aissa, Christophe; The Journal of organic chemistry  (2019) –; doi:10.1021/acs.joc.9b03032

data_4037707
_publ_section_title
;
 Palladium-Catalyzed Synthesis of \a-Carbonyl-\a'-(Hetero)aryl Sulfoxonium
 Ylides: Scope and Insight into the Mechanism.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03032
_journal_year                    2019
_chemical_formula_moiety         'C80 H106 Br2 F6 P2 Pd2'
_chemical_formula_sum            'C80 H106 Br2 F6 P2 Pd2'
_chemical_formula_weight         1616.20
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                76.5013(16)
_cell_angle_beta                 80.0816(16)
_cell_angle_gamma                80.5167(15)
_cell_formula_units_Z            1
_cell_length_a                   9.09016(17)
_cell_length_b                   13.0151(2)
_cell_length_c                   18.0663(4)
_cell_measurement_reflns_used    53885
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.2580
_cell_measurement_theta_min      4.7270
_cell_volume                     2029.92(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4607
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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   -112.00 -15.00   1.00    3.00    --  -41.77 -57.00-180.00   97
  2  \w    -68.00  28.00   1.00    3.00    --  -41.77  57.00-150.00   96
  3  \w   -114.00 -19.00   1.00    3.00    --  -41.77 -38.00-120.00   95
  4  \w   -114.00 -19.00   1.00    3.00    --  -41.77 -38.00  60.00   95
  5  \w     23.00  97.00   1.00    3.00    --   41.77-125.00 -30.00   74
  6  \w     23.00  97.00   1.00    3.00    --   41.77-125.00  90.00   74
  7  \w     10.00 116.00   1.00    3.00    --   41.77  77.00 -60.00  106
  8  \w      8.00  35.00   1.00    3.00    --   42.00  86.00  17.61   27
  9  \w     13.00  45.00   1.00    3.00    --   46.00  82.00-156.59   32
 10  \w     13.00  40.00   1.00    3.00    --   46.00  83.00  93.94   27
 11  \w     18.00  49.00   1.00    3.00    --   50.00  78.00 -26.93   31
 12  \w     22.00  49.00   1.00    3.00    --   54.00  78.00   7.40   27
 13  \w     31.00 135.00   1.00    3.00    --   62.00  76.00 104.15  104
 14  \w     35.00 139.00   1.00    3.00    --   66.00  75.00 -32.55  104
 15  \w     35.00 139.00   1.00    3.00    --   66.00  76.00 176.84  104
 16  \w     35.00 139.00   1.00    3.00    --   66.00  74.00 136.69  104
 17  \w     35.00 140.00   1.00    3.00    --   66.00  77.00  76.17  105
 18  \w     35.00 139.00   1.00    3.00    --   66.00  75.00-127.86  104
 19  \w     35.00 140.00   1.00    3.00    --   66.00  77.00 -67.81  105
 20  \w     35.00 140.00   1.00    3.00    --   66.00  77.00-104.37  105
 21  \w     39.00 144.00   1.00    3.00    --   70.00  77.00  23.26  105
 22  \w     80.00 178.00   1.00   12.00    --  111.00  77.00 120.00   98
 23  \w     41.00 139.00   1.00   12.00    --  111.00 -61.00  30.00   98
 24  \w     83.00 178.00   1.00   12.00    --  111.00  61.00-120.00   95
 25  \w     80.00 178.00   1.00   12.00    --  111.00  77.00  30.00   98
 26  \w     83.00 178.00   1.00   12.00    --  111.00  61.00   0.00   95
 27  \w     80.00 178.00   1.00   12.00    --  111.00  77.00-180.00   98
 28  \w     36.00 116.00   1.00   12.00    --  111.00-111.00 -60.00   80
 29  \w     30.00 109.00   1.00   12.00    --  111.00 -95.00 -30.00   79
 30  \w     83.00 178.00   1.00   12.00    --  111.00  61.00 120.00   95
 31  \w     83.00 178.00   1.00   12.00    --  111.00  61.00  90.00   95
 32  \w     83.00 178.00   1.00   12.00    --  111.00  61.00 150.00   95
 33  \w     30.00 109.00   1.00   12.00    --  111.00 -95.00  60.00   79
 34  \w     80.00 178.00   1.00   12.00    --  111.00  77.00 -90.00   98
 35  \w     36.00 116.00   1.00   12.00    --  111.00-111.00-150.00   80
 36  \w     30.00 109.00   1.00   12.00    --  111.00 -95.00 120.00   79
 37  \w     80.00 178.00   1.00   12.00    --  111.00  77.00 -60.00   98
 38  \w     80.00 178.00   1.00   12.00    --  111.00  77.00   0.00   98
 39  \w     80.00 178.00   1.00   12.00    --  111.00  77.00  90.00   98
 40  \w     80.00 178.00   1.00   12.00    --  111.00  77.00-120.00   98
 41  \w     83.00 178.00   1.00   12.00    --  111.00  61.00-180.00   95
 42  \w     83.00 178.00   1.00   12.00    --  111.00  61.00  60.00   95
 43  \w     83.00 178.00   1.00   12.00    --  111.00  61.00-150.00   95
 44  \w     83.00 178.00   1.00   12.00    --  111.00  61.00  30.00   95
 45  \w     41.00 139.00   1.00   12.00    --  111.00 -61.00-180.00   98
 46  \w     83.00 178.00   1.00   12.00    --  111.00  61.00 -90.00   95
 47  \w     36.00 116.00   1.00   12.00    --  111.00-111.00  30.00   80
 48  \w     80.00 178.00   1.00   12.00    --  111.00  77.00  60.00   98
 49  \w     80.00 178.00   1.00   12.00    --  111.00  77.00-150.00   98
 50  \w     83.00 178.00   1.00   12.00    --  111.00  61.00 -60.00   95
 51  \w     83.00 178.00   1.00   12.00    --  111.00  61.00 -30.00   95
 52  \w     80.00 178.00   1.00   12.00    --  111.00  77.00 -30.00   98
 53  \w     80.00 178.00   1.00   12.00    --  111.00  77.00 150.00   98
 54  \w   -114.00 -19.00   1.00    3.00    --  -41.77 -38.00 -60.00   95
 55  \w     15.00 112.00   1.00    3.00    --   41.77  57.00-180.00   97
 56  \w      7.00  33.00   1.00    3.00    --   42.00  88.00 157.37   26
 57  \w     18.00  46.00   1.00    3.00    --   50.00  81.00 -92.04   28
 58  \w     17.00  45.00   1.00    3.00    --   50.00  82.00 145.30   28
 59  \w     17.00  45.00   1.00    3.00    --   50.00  82.00  31.78   28
 60  \w     23.00 127.00   1.00    3.00    --   54.00  75.00 -98.51  104
 61  \w     22.00  49.00   1.00    3.00    --   54.00  78.00  75.24   27
 62  \w     23.00 127.00   1.00    3.00    --   54.00  76.00 -64.92  104
 63  \w     22.00  49.00   1.00    3.00    --   54.00  78.00-123.20   27
 64  \w     27.00 132.00   1.00    3.00    --   58.00  77.00 126.61  105
 65  \w     27.00 131.00   1.00    3.00    --   58.00  75.00-161.44  104
 66  \w     31.00 136.00   1.00    3.00    --   62.00  77.00 -12.15  105
 67  \w     31.00 135.00   1.00    3.00    --   62.00  76.00  23.14  104
 68  \w     31.00 135.00   1.00    3.00    --   62.00  75.00 115.57  104
 69  \w     31.00 135.00   1.00    3.00    --   62.00  76.00-147.10  104
 70  \w     31.00 135.00   1.00    3.00    --   62.00  76.00  78.08  104
 71  \w     35.00 140.00   1.00    3.00    --   66.00  77.00 151.67  105
 72  \w     35.00 139.00   1.00    3.00    --   66.00  76.00  49.79  104
 73  \w     87.00 178.00   1.00   12.00    --  111.00  45.00-120.00   91
 74  \w     87.00 178.00   1.00   12.00    --  111.00  45.00-150.00   91
 75  \w    100.00 178.00   1.00   12.00    --  111.00 111.00  90.00   78
 76  \w     87.00 178.00   1.00   12.00    --  111.00  45.00   0.00   91
 77  \w     87.00 178.00   1.00   12.00    --  111.00  45.00 -90.00   91
 78  \w     41.00 139.00   1.00   12.00    --  111.00 -61.00-150.00   98
 79  \w     87.00 137.00   1.00   12.00    --  111.00  45.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0961125000
_diffrn_orient_matrix_UB_12      0.1001829000
_diffrn_orient_matrix_UB_13      -0.0392833000
_diffrn_orient_matrix_UB_21      0.1305918000
_diffrn_orient_matrix_UB_22      0.0654737000
_diffrn_orient_matrix_UB_23      -0.0079630000
_diffrn_orient_matrix_UB_31      0.0617861000
_diffrn_orient_matrix_UB_32      -0.0273806000
_diffrn_orient_matrix_UB_33      -0.0789712000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0759
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            87802
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.569
_diffrn_reflns_theta_min         3.522
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.518
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.156
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.322
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.227
_exptl_crystal_size_min          0.058
_refine_diff_density_max         1.172
_refine_diff_density_min         -0.883
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     449
_refine_ls_number_reflns         8477
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0353
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0603P)^2^+1.9971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0988
_refine_ls_wR_factor_ref         0.0995
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8331
_reflns_number_total             8477
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03032_si_002.cif
_cod_data_source_block           ca105
_cod_original_cell_volume        2029.93(7)
_cod_database_code               4037707
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C86 H112 Br2 O2 P2 Pd2 F3'
_chemical_oxdiff_usercomment     CJA-06-101-00
_diffrn_oxdiff_digest_frames
;
015ab56c8eca23e67e6ec741ddd0f27fbe068135c63
;
_diffrn_oxdiff_digest_hkl
;
01e5515887b03984a5bdae64b9545cba17bd9f
;
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F3A-C40 \\sim F2-C40 \\sim F2A-C40 \\sim F1-C40 \\sim F1A-C40 \\sim F3-C40
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F2) \\sim Ueq, Uanis(F3A) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F1A)
\\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2A) \\sim Ueq: with sigma of 0.002 and
sigma for terminal atoms of 0.004
4. Others
 Sof(F3A)=Sof(F2A)=Sof(F1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C13(H13), C16(H16), C19(H19), C22(H22), C28(H28)
5.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,
 H27B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B),
 C33(H33A,H33B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C11(H11), C35(H35), C36(H36),
 C38(H38), C39(H39)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              68284
_shelx_hkl_checksum              68292
_shelx_fab_checksum              66164
_olex2_date_sample_data_collection 2019-07-09
_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 1.639
_oxdiff_exptl_absorpt_empirical_full_min 0.682