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_1547834
_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         'C24 H29 N O5 S'
_chemical_formula_sum            'C24 H29 N O5 S'
_chemical_formula_weight         443.54
_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             2017-09-26
_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                 113.393(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5447(7)
_cell_length_b                   17.0612(9)
_cell_length_c                   12.4930(8)
_cell_measurement_reflns_used    8197
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      30.9350
_cell_measurement_theta_min      2.1460
_cell_volume                     2258.4(3)
_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   -110.00  25.00   0.50   10.00    --  -20.00   0.00 -36.00  270
  2  \w   -110.00  10.00   0.50   10.00    --  -20.00 -72.00 -36.00  240
  3  \w    -71.00  19.00   0.50   10.00    --  -20.00 -72.00 108.00  180
  4  \w    -35.00  19.00   0.50   10.00    --  -20.00 -72.00-180.00  108
  5  \w    -59.00 -39.50   0.50   10.00    --  -20.00  72.00 108.00   39
;
_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      0.0294626000
_diffrn_orient_matrix_UB_12      -0.0320832000
_diffrn_orient_matrix_UB_13      0.0368421000
_diffrn_orient_matrix_UB_21      -0.0069061000
_diffrn_orient_matrix_UB_22      0.0193194000
_diffrn_orient_matrix_UB_23      0.0474674000
_diffrn_orient_matrix_UB_31      -0.0596211000
_diffrn_orient_matrix_UB_32      -0.0181034000
_diffrn_orient_matrix_UB_33      -0.0148151000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1040
_diffrn_reflns_av_unetI/netI     0.0696
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            17412
_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         2.034
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.179
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82855
_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    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.475
_refine_diff_density_min         -0.649
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         3979
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0576
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0764P)^2^+1.3577P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1417
_refine_ls_wR_factor_ref         0.1548
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3257
_reflns_number_total             3979
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sjg-anu-8.cif
_cod_data_source_block           sjg-anu-4-37_a_mo
_cod_depositor_comments
'Adding full bibliography for 1547825--1547834.cif.'
_cod_database_code               1547834
_reflns_odcompleteness_completeness 93.23
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.00
_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:
 C24(H24), C8(H8), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C15(H15A,H15B), C23(H23A,H23B), C17(H17A,H17B), C22(H22A,
 H22B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C4(H4), C10(H10), C3(H3), C13(H13), C7(H7), C11(H11), C12(H12)
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 2.131
_oxdiff_exptl_absorpt_empirical_full_min 0.469