Synthesis of Benzo[1,4]heterocycles using Palladium Catalyzed Heck Reaction to Vinylogous Carbonates/Carbamates: Unexpected Formation of Indoles via Carbopalladation Intercepted by Nucleopalladation.
Gharpure, Santosh J.; Anuradha, Dandela; Organic letters 19 (2017) 6136–6139; doi:10.1021/acs.orglett.7b03016

data_1547831
_publ_section_title
;
 Synthesis of Benzo[1,4]heterocycles using Palladium Catalyzed Heck
 Reaction to Vinylogous Carbonates/Carbamates: Unexpected Formation of
 Indoles via Carbopalladation Intercepted by Nucleopalladation.
;
_journal_issue                   22
_journal_name_full               'Organic letters'
_journal_page_first              6136
_journal_page_last               6139
_journal_paper_doi               10.1021/acs.orglett.7b03016
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C17 H20 O3 S'
_chemical_formula_sum            'C17 H20 O3 S'
_chemical_formula_weight         304.39
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-25
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.08.26 svn.r3337 for Rigaku Oxford Diffraction, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.657(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.5546(3)
_cell_length_b                   22.9756(9)
_cell_length_c                   13.1098(5)
_cell_measurement_reflns_used    12200
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      31.2940
_cell_measurement_theta_min      1.9100
_cell_volume                     3142.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -59.00  70.00   0.50   16.00    --  -20.00  72.00  36.00  258
  2  \w   -110.00 -28.00   0.50   16.00    --  -20.00   0.00 108.00  164
  3  \w    -41.00  -9.00   0.50   16.00    --  -20.00  72.00 -36.00   64
  4  \w     38.00  68.50   0.50   16.00    --  -20.00  72.00-108.00   61
  5  \w    -85.00  27.00   0.50   16.00    --  -20.00   0.00  36.00  224
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0286663000
_diffrn_orient_matrix_UB_12      0.0280069000
_diffrn_orient_matrix_UB_13      0.0054918000
_diffrn_orient_matrix_UB_21      -0.0412703000
_diffrn_orient_matrix_UB_22      0.0077368000
_diffrn_orient_matrix_UB_23      0.0357145000
_diffrn_orient_matrix_UB_31      0.0457789000
_diffrn_orient_matrix_UB_32      -0.0104856000
_diffrn_orient_matrix_UB_33      0.0410749000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0601
_diffrn_reflns_av_unetI/netI     0.0478
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            22626
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.804
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.213
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75121
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
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    1.287
_exptl_crystal_description       plate
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.321
_exptl_crystal_size_min          0.097
_refine_diff_density_max         0.652
_refine_diff_density_min         -0.762
_refine_diff_density_rms         0.240
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         5547
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.147
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0448
_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^)+(0.0964P)^2^+0.5795P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1254
_refine_ls_wR_factor_ref         0.1641
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4689
_reflns_number_total             5547
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sjg-anu-3.cif
_cod_data_source_block           sjg-anu-s-o_mo
_cod_depositor_comments
'Adding full bibliography for 1547825--1547834.cif.'
_cod_database_code               1547831
_chemical_oxdiff_formula         'C17 H20 O3 S1'
_reflns_odcompleteness_completeness 90.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.07
_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.a Ternary CH refined with riding coordinates:
 C28(H28), C6(H6), C23(H23), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C10(H10A,H10B), C7(H7A,H7B), C24(H24A,H24B), C26(H26A,H26B),
 C19(H19A,H19B), C2(H2A,H2B), C25(H25A,H25B), C9(H9A,H9B), C8(H8A,H8B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C21(H21), C33(H33), C13(H13), C15(H15), C14(H14), C31(H31), C32(H32),
 C16(H16), C30(H30)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C1(H1A,H1B,H1C)
;
_shelx_shelxl_version_number     2014/7
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.416
_oxdiff_exptl_absorpt_empirical_full_min 0.678