Synthesis of [3a,7a]-Dihydroindoles by a Tandem Arene Cyclopropanation/3,5-Sigmatropic Rearrangement Reaction.
Wilkerson-Hill, Sidney M; Haines, Brandon E.; Musaev, Djamaladdin G.; Davies, Huw M. L.; The Journal of organic chemistry 83 (2018) 7939–7949; doi:10.1021/acs.joc.8b00812

data_4035564
_publ_section_title
;
 Synthesis of [3a,7a]-Dihydroindoles by a Tandem Arene
 Cyclopropanation/3,5-Sigmatropic Rearrangement Reaction.
;
_journal_issue                   15
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7939
_journal_page_last               7949
_journal_paper_doi               10.1021/acs.joc.8b00812
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C19 H18 N2 O4 S'
_chemical_formula_sum            'C19 H18 N2 O4 S'
_chemical_formula_weight         370.41
_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     dual
_audit_creation_date             2017-12-12
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.11.20 svn.r3469 for OlexSys, GUI svn.r5431)
;
_cell_angle_alpha                85.531(6)
_cell_angle_beta                 80.177(5)
_cell_angle_gamma                81.927(5)
_cell_formula_units_Z            4
_cell_length_a                   7.430(2)
_cell_length_b                   12.034(3)
_cell_length_c                   21.281(6)
_cell_measurement_reflns_used    2110
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.16
_cell_measurement_theta_min      2.81
_cell_volume                     1853.5(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2  v2014.11 (Bruker, 2014)'
_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-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT-2014/4 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1174
_diffrn_reflns_av_unetI/netI     0.1361
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            22782
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.349
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         1.945
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           35
_diffrn_source_voltage           45
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.201
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6492
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1553 before and 0.0700 after correction. The Ratio of minimum to maximum transmission is 0.8708. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       needle
_exptl_crystal_F_000             776
_exptl_crystal_recrystallization_method
'The material was recrystallised from diethyl ether by slow evaporation'
_exptl_crystal_size_max          0.605
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.126
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.395
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         6746
_refine_ls_number_restraints     228
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.1538
_refine_ls_R_factor_gt           0.0776
_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^)+(0.0261P)^2^+5.1516P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1323
_refine_ls_wR_factor_ref         0.1665
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3818
_reflns_number_total             6746
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00812_si_002.cif
_cod_data_source_block           smhii-038c-f39-54
_cod_original_cell_volume        1853.3(9)
_cod_database_code               4035564
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.888
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 O27, O26, N14, C18, C15, C5, C19, C17, C16, C20, C21, C22
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1, N2, C5, C3, C10, C9, C4, C13, C7, C8, C23, C6, O24, O12, C25
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C20, S1, O24, O12, N2, C25, C3, C6, H25A, H25B, H25C, C4, C13, C7, C5, H6,
 C10, H4, H13A, H13B, H13C, H7, C8, N14, H10, C9, H8, C18, C15, C23, O27, C17,
 O26, C16, H23A, H23B, H23C, C22, C19, H22, C21, H19, H21, H20
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3.a Ternary CH refined with riding coordinates:
 C4'(H4'), C4(H4)
3.b Aromatic/amide H refined with riding coordinates:
 C6'(H6'), C19(H19), C6(H6), C22(H22), C10(H10), C10'(H10'), C20(H20),
 C21(H21), C19'(H19'), C7'(H7'), C22'(H22'), C21'(H21'), C20'(H20'), C8'(H8'),
 C7(H7), C8(H8)
3.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C25(H25A,H25B,H25C), C25'(H25D,H25E,H25F), C23'(H23D,
 H23E,H23F), C13'(H13D,H13E,H13F), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              47499
_shelx_hkl_checksum              43856
_shelx_fab_checksum              76624
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id SMHII-038C-F39-54
_olex2_submission_special_instructions 'No special instructions were received'