Transformations of Conjugated Enynones in the Superacid CF3SO3H. Synthesis of Butadienyl Triflates, Indanones, and Indenes.
Saulnier, Steve; Golovanov, Alexander A.; Ivanov, Alexandr Yu; Boyarskaya, Irina A.; Vasilyev, Aleksander V.; The Journal of organic chemistry 81 (2016) 1967–1980; doi:10.1021/acs.joc.5b02785

data_4036568
_publ_section_title
;
 Transformations of Conjugated Enynones in the Superacid CF3SO3H.
 Synthesis of Butadienyl Triflates, Indanones, and Indenes.
;
_journal_issue                   5
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1967
_journal_page_last               1980
_journal_paper_doi               10.1021/acs.joc.5b02785
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C18 H12 Cl F3 O4 S'
_chemical_formula_sum            'C18 H12 Cl F3 O4 S'
_chemical_formula_weight         416.79
_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     iterative
_audit_creation_date             2015-08-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 102.696(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.6536(18)
_cell_length_b                   8.4595(6)
_cell_length_c                   10.5343(9)
_cell_measurement_reflns_used    4474
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.0920
_cell_measurement_theta_min      4.3850
_cell_volume                     1795.5(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector_area_resol_mean 10.3829
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -13.00   35.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162   38.0000 -180.0000 48

  2 omega -127.00  -44.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162 -178.0000  120.0000 83

  3 omega -111.00  -22.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162  -38.0000   30.0000 89

  4 omega   28.00   69.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       39.8162  -57.0000  -90.0000 41

  5 omega   72.00   99.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       39.8162 -137.0000   47.0000 27

  6 omega  101.00  127.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -137.0000   47.0000 26

  7 omega   41.00   92.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000 -120.0000 51

  8 omega   35.00   80.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000 -120.0000 45

  9 omega   35.00   62.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000    0.0000 27

 10 omega  110.00  166.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   15.0000  -30.0000 56

 11 omega   36.00   63.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000  -60.0000 27

 12 omega   39.00   78.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -137.0000   47.0000 39

 13 omega  112.00  140.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  -30.0000 28

 14 omega   67.00   93.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000 -150.0000 26

 15 omega   39.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000    0.0000 59

 16 omega   78.00  147.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000 -180.0000 69

 17 omega   39.00   74.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000   60.0000 35

 18 omega   53.00   96.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   15.0000  -30.0000 43

 19 omega   36.00   79.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000    0.0000 43

 20 omega   97.00  148.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000  150.0000 51

 21 omega   43.00   82.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000 -180.0000 39

 22 omega   41.00   87.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000   90.0000 46

 23 omega   46.00   71.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000   90.0000 25

 24 omega   88.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000  -60.0000 27

 25 omega   62.00  126.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000  -30.0000 64

 26 omega   30.00   90.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000  150.0000 60

 27 omega   95.00  167.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000 -150.0000 72

 28 omega   86.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -91.0000  100.7128 25

 29 omega   62.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000 -150.0000 53

 30 omega  106.00  131.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000  -60.0000 25

 31 omega   77.00  102.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000 -150.0000 25

 32 omega   90.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000 -120.0000 25

 33 omega  100.00  125.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -133.0000 -134.0000 25

 34 omega   51.00   78.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -91.0000  100.7128 27

 35 omega -102.00  -48.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162  178.0000  -60.0000 54

 36 omega  -64.00  -37.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162  178.0000    0.0000 27

 37 omega  -49.00   28.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162   38.0000  150.0000 77

 38 omega    0.00   27.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162   38.0000 -150.0000 27

 39 omega -118.00  -91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.8162  178.0000    0.0000 27

 40 omega   84.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -90.0000  127.1658 27

 41 omega   75.00  102.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -68.0000   67.3870 27

 42 omega   47.00  117.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -115.0000  145.2688 70

 43 omega  100.00  133.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000    0.0000 33

 44 omega  119.00  146.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -150.0000 27

 45 omega   65.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  -60.0000 33

 46 omega   44.00   69.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  150.0000 25

 47 omega   74.00   99.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  150.0000 25

 48 omega  114.00  141.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000   30.0000 27

 49 omega   39.00   64.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -68.0000   67.3870 25

 50 omega   86.00  113.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -180.0000 27

 51 omega   87.00  114.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000    0.0000 27

 52 omega   37.00   70.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -112.0000  -30.0000 33

 53 omega   62.00  100.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -61.0000  -30.0000 38

 54 omega  152.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000 -150.0000 25

 55 omega   91.00  121.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -77.0000 -120.0000 30

 56 omega   99.00  142.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   15.0000 -180.0000 43

 57 omega   84.00  129.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   90.0000 45

 58 omega  135.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000   90.0000 42

 59 omega  102.00  133.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000  -30.0000 31

 60 omega  151.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000  -30.0000 27

 61 omega   30.00   62.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000   60.0000 32

 62 omega   77.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000   60.0000 31

 63 omega   47.00   91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000   90.0000 44

 64 omega   49.00   76.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -30.0000  120.0000 27

 65 omega   88.00  131.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   45.0000  150.0000 43

 66 omega   63.00   88.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000  150.0000 25

 67 omega  102.00  156.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  112.0000   30.0000 54

 68 omega   58.00   97.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  178.0000   30.0000 39

 69 omega   60.00   87.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -27.0000 -157.3084 27

 70 omega  136.00  163.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   30.0000    0.0000 27

 71 omega   78.00  125.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -133.0000   93.2353 47

 72 omega  144.00  171.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   77.0000 -180.0000 27

 73 omega   98.00  123.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000 -128.0000  -68.8150 25

 74 omega   39.00   79.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -45.0000  -30.0000 40

 75 omega   83.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000  -90.0000 26

 76 omega   84.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000  -95.0000   30.0000 25

 77 omega   85.00  104.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      113.0000   61.0000  -90.0000 19
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0586376000
_diffrn_orient_matrix_UB_12      0.0360712000
_diffrn_orient_matrix_UB_13      -0.1145261000
_diffrn_orient_matrix_UB_21      0.0118113000
_diffrn_orient_matrix_UB_22      0.1785980000
_diffrn_orient_matrix_UB_23      0.0232674000
_diffrn_orient_matrix_UB_31      0.0475577000
_diffrn_orient_matrix_UB_32      0.0000944000
_diffrn_orient_matrix_UB_33      -0.0939328000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1952
_diffrn_reflns_av_unetI/netI     0.0507
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            24989
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.999
_diffrn_reflns_theta_min         4.389
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.463
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45169
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brownish
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_density_diffrn    1.542
_exptl_crystal_description
;
;
_exptl_crystal_F_000             848
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.835
_refine_diff_density_min         -0.609
_refine_diff_density_rms         0.109
_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     244
_refine_ls_number_reflns         3411
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.1054
_refine_ls_R_factor_gt           0.0934
_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^)+(0.0582P)^2^+13.6936P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1937
_refine_ls_wR_factor_ref         0.2041
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2804
_reflns_number_total             3411
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b02785_si_001.cif
_cod_data_source_block           179_b
_cod_database_code               4036568
_chemical_oxdiff_formula         'N4 C20 O4'
_reflns_odcompleteness_completeness 94.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C9(H9), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19), C1A(H1A), C1B(H1B)
;
_shelx_res_checksum              64919
_shelx_hkl_checksum              76564
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'