Doubleisomerization / cycloisomerization / aromatization of 1-(allyloxy)-2-(cyclopropylmethyl)benzenes to give 2-ethyl-3-isopropylbenzofurans using multitasking single rhodium catalyst
Sato, Yuta; Matsuzaki, Tsuyoshi; Takehara, Tsunayoshi; Sako, Makoto; Suzuki, Takeyuki; Arisawa, Mitsuhiro; Chemical Communications  (2021) –; doi:10.1039/D1CC06163A

data_7129332
_publ_section_title
;
 Doubleisomerization / cycloisomerization / aromatization of
 1-(allyloxy)-2-(cyclopropylmethyl)benzenes to give
 2-ethyl-3-isopropylbenzofurans using multitasking single rhodium catalyst
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06163A
_journal_year                    2021
_chemical_formula_moiety         'C20 H23 N O2 S'
_chemical_formula_sum            'C20 H23 N O2 S'
_chemical_formula_weight         341.45
_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             2021-09-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-10-20 deposited with the CCDC.	2021-12-01 downloaded from the CCDC.
;
_cell_angle_alpha                70.9170(10)
_cell_angle_beta                 82.7930(10)
_cell_angle_gamma                79.8760(10)
_cell_formula_units_Z            4
_cell_length_a                   9.56190(10)
_cell_length_b                   11.8973(2)
_cell_length_c                   17.1330(3)
_cell_measurement_reflns_used    19171
_cell_measurement_temperature    103.15
_cell_measurement_theta_max      75.4350
_cell_measurement_theta_min      3.9480
_cell_volume                     1808.43(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      103.15
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.977
_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   -124.00  -1.00   0.50    0.50    --  -35.00 -60.00-142.00  246
  2  \w    -68.00  54.00   0.50    0.50    --  -35.00  60.00  -3.00  244
  3  \w     10.00 133.00   0.50    0.50    --   43.60  60.00  -3.00  246
  4  \w    -46.00  78.00   0.50    0.50    --   43.60 -60.00-142.00  248
  5  \w     76.00 199.00   0.50    0.50    --  109.30  60.00  -3.00  246
  6  \w     20.00 144.00   0.50    0.50    --  109.30 -60.00-142.00  248
  7  \w   -124.00 -76.00   0.50    0.50    --  -35.00 -77.00  60.00   96
  8  \w    -39.00   9.00   0.50    0.50    --  -35.00 -82.00 -90.00   96
  9  \w   -124.00 -76.00   0.50    0.50    --  -35.00 -77.00 120.00   96
 10  \w     81.00 133.00   0.50    0.50    --   43.60  82.00 150.00  104
 11  \w      2.00  48.00   0.50    0.50    --   43.60  77.00 150.00   92
 12  \w      2.00  48.00   0.50    0.50    --   43.60  77.00 -60.00   92
 13  \w      2.00  48.00   0.50    0.50    --   43.60  77.00-150.00   92
 14  \w      2.00  48.00   0.50    0.50    --   43.60  77.00 120.00   92
 15  \w      2.00  48.00   0.50    0.50    --   43.60  77.00 -90.00   92
 16  \w     81.00 133.00   0.50    0.50    --   43.60  82.00  60.00  104
 17  \w      2.00  48.00   0.50    0.50    --   43.60  77.00  90.00   92
 18  \w     20.00 154.00   0.50    0.50    --  109.30 -82.00 -30.00  268
 19  \w     20.00 154.00   0.50    0.50    --  109.30 -82.00 120.00  268
 20  \w     66.00 199.00   0.50    0.50    --  109.30  38.00  41.79  266
 21  \w     20.00 154.00   0.50    0.50    --  109.30 -82.00   0.00  268
 22  \w     20.00 154.00   0.50    0.50    --  109.30 -82.00-150.00  268
 23  \w     20.00 154.00   0.50    0.50    --  109.30 -82.00  60.00  268
 24  \w     20.00 154.00   0.50    0.50    --  109.30 -82.00 -90.00  268
 25  \w     20.00 199.00   0.50    0.50    --  109.30  15.00-180.00  358
 26  \w     70.00 199.00   0.50    0.50    --  109.30  45.00 -60.00  258
 27  \w     72.00 199.00   0.50    0.50    --  109.30  46.00-147.29  254
 28  \w     82.00 199.00   0.50    0.50    --  109.30  82.00 -90.00  234
 29  \w     20.00 154.00   0.50    0.50    --  109.30 -82.00 150.00  268
 30  \w     20.00 144.00   0.50    0.50    --  109.30 -61.00  30.00  248
 31  \w    -46.00  77.00   0.50    0.50    --   43.60 -57.00  60.00  246
 32  \w     81.00 133.00   0.50    0.50    --   43.60  82.00-120.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB PRO'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1418346000
_diffrn_orient_matrix_UB_12      -0.0730248000
_diffrn_orient_matrix_UB_13      -0.0198702000
_diffrn_orient_matrix_UB_21      0.0705447000
_diffrn_orient_matrix_UB_22      0.0317335000
_diffrn_orient_matrix_UB_23      0.0646159000
_diffrn_orient_matrix_UB_31      -0.0428444000
_diffrn_orient_matrix_UB_32      -0.1132711000
_diffrn_orient_matrix_UB_33      0.0673153000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0212
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            34553
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.671
_diffrn_reflns_theta_min         3.973
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    1.673
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.600
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       plate
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.466
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     461
_refine_ls_number_reflns         7332
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.0371
_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^)+(0.0469P)^2^+0.8334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0979
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6858
_reflns_number_total             7332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06163a3.cif
_cod_data_source_block           ntsp_1
_cod_database_code               7129332
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C40 H46 N2 S2 O4'
_chemical_oxdiff_usercomment     '-170oC, grease, MicroMount'
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.742
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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, All C(H,H,H,H,H,H) groups
2. Rigid body (RIGU) restrains
 C37, C36
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Others
 Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C12A)=Sof(H12A)=Sof(C14A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=1-FVAR(1)
 Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C12)=Sof(H12)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C42(H42), C12(H12), C12A(H12A)
4.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C40(H40A,H40B)
4.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C23(H23), C22(H22), C8(H8), C19(H19), C39(H39), C49(H49), C20(H20),
 C6(H6), C7(H7), C52(H52), C50(H50), C53(H53), C37(H37), C38(H38), C36(H36)
4.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C24(H24A,H24B,H24C), C13(H13A,H13B,H13C), C13(H13D,H13E,
 H13F), C43(H43A,H43B,H43C), C54(H54A,H54B,H54C), C44(H44A,H44B,H44C), C41(H41A,
 H41B,H41C), C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F)
;
_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 1.257
_oxdiff_exptl_absorpt_empirical_full_min 0.876