Experimental and Computational Study of the ( Z)-Selective Formation of Trisubstituted Olefins and Benzo-Fused Oxacycles from the Ruthenium-Catalyzed Dehydrative C-H Coupling of Phenols with Ketones.
Lee, Hanbin; Mane, Manoj V.; Ryu, Ho; Sahu, Debashis; Baik, Mu-Hyun; Yi, Chae S.; Journal of the American Chemical Society 140 (2018) 10289–10296; doi:10.1021/jacs.8b05875

data_4132736
_publ_section_title
;
 Experimental and Computational Study of the ( Z)-Selective Formation of
 Trisubstituted Olefins and Benzo-Fused Oxacycles from the
 Ruthenium-Catalyzed Dehydrative C-H Coupling of Phenols with Ketones.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10289
_journal_page_last               10296
_journal_paper_doi               10.1021/jacs.8b05875
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C14 H18 O4'
_chemical_formula_sum            'C14 H18 O4'
_chemical_formula_weight         250.28
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-08-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 91.2110(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.53828(6)
_cell_length_b                   24.4737(4)
_cell_length_c                   8.98955(14)
_cell_measurement_reflns_used    7205
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.1430
_cell_measurement_theta_min      4.9030
_cell_volume                     1218.19(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3756
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_details
;
  1 omega  -71.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3987   57.0000  -90.0000 104

  2 omega -124.00  -79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3987  -99.0000 -180.0000 45

  3 omega -124.00  -79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3987  -99.0000 -120.0000 45

  4 omega   23.00   99.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.3987 -125.0000   30.0000 76

  5 omega   30.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -30.0000    0.0000 60

  6 omega   30.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -30.0000  -60.0000 60

  7 omega   34.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -45.0000  -90.0000 64

  8 omega   78.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878   61.0000 -180.0000 100

  9 omega   30.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -30.0000 -150.0000 60

 10 omega   34.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -45.0000   60.0000 64

 11 omega   30.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -30.0000  120.0000 60

 12 omega   33.00  122.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878 -125.0000  -60.0000 89

 13 omega -115.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3987  -57.0000   60.0000 103

 14 omega -115.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3987  -57.0000 -180.0000 103

 15 omega -115.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3987  -57.0000  -60.0000 103

 16 omega   78.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878   30.0000  -90.0000 100

 17 omega   78.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878   30.0000  120.0000 100

 18 omega   24.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878  -94.0000   60.0000 85

 19 omega   75.00  147.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878   77.0000   30.0000 72

 20 omega   47.00  178.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.2878   15.0000   30.0000 131
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0516337000
_diffrn_orient_matrix_UB_12      0.0449919000
_diffrn_orient_matrix_UB_13      -0.1149388000
_diffrn_orient_matrix_UB_21      0.2715766000
_diffrn_orient_matrix_UB_22      -0.0034073000
_diffrn_orient_matrix_UB_23      0.0397037000
_diffrn_orient_matrix_UB_31      0.0317528000
_diffrn_orient_matrix_UB_32      -0.0439160000
_diffrn_orient_matrix_UB_33      -0.1207168000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            11890
_diffrn_reflns_theta_full        72.00
_diffrn_reflns_theta_max         73.92
_diffrn_reflns_theta_min         3.61
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.816
_exptl_absorpt_correction_T_max  0.985
_exptl_absorpt_correction_T_min  0.931
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.576
_exptl_crystal_size_mid          0.2375
_exptl_crystal_size_min          0.1009
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     338
_refine_ls_number_reflns         4642
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0372
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0647P)^2^+0.1241P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0971
_refine_ls_wR_factor_ref         0.1010
_reflns_number_gt                4360
_reflns_number_total             4642
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja8b05875_si_003.cif
_cod_data_source_block           yi3i
_cod_database_code               4132736
_chemical_oxdiff_formula         'C14 H18 O4'
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.36(14) 0.64(14)
2. 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
3.a Ternary CH refined with riding coordinates:
 C7(H7), C7A(H7A)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C8A(H8AA,H8AB),
 C10A(H10C,H10D), C11A(H11C,H11D), C12A(H12C,H12D)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C2A(H2A), C4A(H4AA)
3.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C13A(H13D,H13E,H13F), C14A(H14D,
 H14E,H14F)
;
_olex2_date_sample_data_collection 2016-08-29
_olex2_date_sample_submission    2016-08-29
_olex2_submission_special_instructions 'No special instructions were received'