Synthesis of Branched Tryptamines via the Domino Cloke-Stevens/Grandberg Rearrangement.
Salikov, Rinat F.; Trainov, Konstantin P.; Levina, Anastasia A.; Belousova, Irina K.; Medvedev, Michael G.; Tomilov, Yury V.; The Journal of organic chemistry 82 (2017) 790–795; doi:10.1021/acs.joc.6b02578

data_4032243
_publ_section_title
;
 Synthesis of Branched Tryptamines via the Domino Cloke-Stevens/Grandberg
 Rearrangement.
;
_journal_issue                   1
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              790
_journal_page_last               795
_journal_paper_doi               10.1021/acs.joc.6b02578
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H19 Br N2 O'
_chemical_formula_sum            'C19 H19 Br N2 O'
_chemical_formula_weight         371.27
_chemical_name_systematic
(S)-N-(2-(5-bromo-2-methyl-1H-indol-3-yl)-1-phenylethyl)acetamide
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-28
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.431(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.1146(11)
_cell_length_b                   19.140(3)
_cell_length_c                   11.5187(16)
_cell_measurement_reflns_used    7176
_cell_measurement_temperature    120
_cell_measurement_theta_max      30.34
_cell_measurement_theta_min      2.68
_cell_volume                     1676.5(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      120
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX DUO CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0837
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            23329
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.716
_diffrn_reflns_theta_min         1.887
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.458
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.2407
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1558 before and 0.0619 after correction.
The Ratio of minimum to maximum transmission is 0.5559.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear brownish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.471
_exptl_crystal_description       prism
_exptl_crystal_F_000             760
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.913
_refine_diff_density_min         -0.511
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 3161 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.898
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     435
_refine_ls_number_reflns         10315
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.898
_refine_ls_R_factor_all          0.0567
_refine_ls_R_factor_gt           0.0382
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0718
_refine_ls_wR_factor_ref         0.0772
_reflns_Friedel_coverage         0.932
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                8145
_reflns_number_total             10315
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02578_si_001.cif
_cod_data_source_block           sad
_cod_database_code               4032243
_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:
 C13(H00M), C13A(H3)
2.b Secondary CH2 refined with riding coordinates:
 C12A(H01F,H01E), C12(H10,H11)
2.c Aromatic/amide H refined with riding coordinates:
 C6A(H013), C17(H00G), C18A(H017), C10A(H00P), C10(H4), C19A(H00X), C15(H00T),
 C19(H5), C15A(H9), C9(H012), C6(H12), C9A(H13), C17A(H14), C18(H15), C16(H019),
  C16A(H19)
2.d Idealised Me refined as rotating group:
 C23(H00H,H00I,H00J), C3(H00N,H00Q,H00S), C3A(H6,H7,H8), C23A(H16,H17,H18)
;
_shelx_res_checksum              88524
_shelx_hkl_checksum              61118
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-07-24
_olex2_date_sample_submission    2016-07-13
_olex2_submission_original_sample_id rinat_2
_olex2_submission_special_instructions 'No special instructions were received'