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_4035565
_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         'C21 H22 N2 O4 S'
_chemical_formula_sum            'C21 H22 N2 O4 S'
_chemical_formula_weight         398.46
_chemical_name_systematic
'[(3aS,7aS)-7a-tert-butyl-1-(methylsulfonyl)-3a,7a-dihydro-1H-indol-3-yl]'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-12-15
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.11.20 svn.r3469 for OlexSys, GUI svn.r5431)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.370(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6680(11)
_cell_length_b                   23.330(3)
_cell_length_c                   8.0236(9)
_cell_measurement_reflns_used    3768
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.4650
_cell_measurement_theta_min      4.1550
_cell_volume                     1970.3(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HyPix
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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 -19.00 50.00 0.50 5.00 -- 0.00 81.00 112.00 138 2 \w -48.00 -5.00 0.50 5.00 -- 0.00 0.00 150.00 86 3 \w -33.00 -7.00 0.50 5.00 -- 0.00 -81.00 -10.00 52 4 \w 30.00 86.00 0.50 20.00 -- 101.17 -57.00 0.00 112 5 \w 51.00 77.00 0.50 15.00 -- 101.17 -81.00 -10.00 52 6 \w 35.00 61.00 0.50 15.00 -- 101.17 -57.00 60.00 52 7 \w 60.00 105.00 0.50 20.00 -- 101.17 -19.00 120.00 90 8 \w 30.00 80.00 0.50 15.00 -- 101.17 -57.00 150.00 100 9 \w 34.00 96.00 0.50 15.00 -- 101.17 -77.00 60.00 124 10 \w 60.00 86.00 0.50 15.00 -- 101.17 0.00 -90.00 52 11 \w 53.00 107.00 0.50 15.00 -- 101.17 0.00-180.00 108 12 \w 121.00 173.00 0.50 20.00 -- 101.17 81.00 112.00 104 13 \w 81.00 116.00 0.50 20.00 -- 101.17 81.00 112.00 70 14 \w -71.00 -45.00 0.50 7.00 -- 0.00 -81.00 -10.00 52 15 \w -88.00 -63.00 0.50 20.00 -- -84.25 -81.00 -10.00 50 16 \w -127.00 -88.00 0.50 20.00 -- -84.25 -19.00 30.00 78 17 \w -79.00 -14.00 0.50 20.00 -- -84.25 38.00 -30.00 130 18 \w -83.00 -58.00 0.50 20.00 -- -84.25 81.00 112.00 50 19 \w -130.00 -83.00 0.50 20.00 -- -84.25 0.00 0.00 94 20 \w -148.00-123.00 0.50 20.00 -- -84.25 -81.00 -10.00 50'
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1630828000
_diffrn_orient_matrix_UB_12      -0.0360083000
_diffrn_orient_matrix_UB_13      -0.0141333000
_diffrn_orient_matrix_UB_21      0.0910085000
_diffrn_orient_matrix_UB_22      -0.0445510000
_diffrn_orient_matrix_UB_23      0.0936705000
_diffrn_orient_matrix_UB_31      -0.0553356000
_diffrn_orient_matrix_UB_32      0.0326524000
_diffrn_orient_matrix_UB_33      0.1116756000
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0734
_diffrn_reflns_av_unetI/netI     0.0735
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            11305
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        65.087
_diffrn_reflns_theta_max         65.087
_diffrn_reflns_theta_min         3.789
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.712
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.795
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35c (Rigaku Oxford Diffraction, 2017)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       plate
_exptl_crystal_F_000             840
_exptl_crystal_recrystallization_method
'The material was recrystallised from ethanol by slow evaporation'
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.374
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         3356
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0815
_refine_ls_R_factor_gt           0.0578
_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^)+(0.0576P)^2^+1.2008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1234
_refine_ls_wR_factor_ref         0.1343
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2625
_reflns_number_total             3356
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b00812_si_005.cif
_cod_data_source_block           smhii-061c-f31-40-rcr_01
_cod_database_code               4035565
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C84  H88  N8  O16  S4  '
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.817
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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
 C1, C9, C10, C12, C11
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1, C9, C5, C6, C7, C8, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N1, C1, C2, C3, N2, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N1, S1, C21, O2, O1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C17, C14, C15, C20, C19, C18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13, O3
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C16, O4
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 N2, C3
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C9, C11
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C9, C12
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C9, C10
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C1, N1, C4
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 O1, S1
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 S1, O2
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
3.a Ternary CH refined with riding coordinates:
 C2(H2)
3.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C20(H20), C6(H6), C17(H17), C7(H7), C8(H8), C19(H19), C18(H18)
3.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C21(H21A,H21B,
 H21C)
;
_shelx_res_checksum              44435
_shelx_hkl_checksum              50124
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with paratone oil'
_olex2_submission_original_sample_id SMHII-061C-F331-40
_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 2.988
_oxdiff_exptl_absorpt_empirical_full_min 0.526