Catalytic Enantioselective Transannular Morita-Baylis-Hillman Reaction.
Mato, Raquel; Manzano, Rubén; Reyes, Efraim; Carrillo, Luisa; Uria, Uxue; Vicario, Jose L.; Journal of the American Chemical Society 141 (2019) 9495–9499; doi:10.1021/jacs.9b03679

data_4127472
_publ_section_title
;
 Catalytic Enantioselective Transannular Morita-Baylis-Hillman Reaction.
;
_journal_issue                   24
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9495
_journal_page_last               9499
_journal_paper_doi               10.1021/jacs.9b03679
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_compound_source        'synthesis as described'
_chemical_formula_moiety         'C11 H16 O2'
_chemical_formula_sum            'C11 H16 O2'
_chemical_formula_weight         180.24
_chemical_name_systematic
;
 (8S,8aS)-8a-hydroxy-8-methyl-2,5,6,7,8,8a-hexahydroazulen-4(1H)-one
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-01-30T09:22:43-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.12324(7)
_cell_length_b                   8.00568(7)
_cell_length_c                   17.09534(15)
_cell_measurement_reflns_used    12795
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.986
_cell_measurement_theta_min      5.522
_cell_volume                     974.885(15)
_computing_cell_refinement
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
        (compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
        (compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
        (compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector_area_resol_mean 5.2012
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
  1 omega -118.00  -83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -99.0000 -150.0000 35

  2 omega  -70.00   32.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256   57.0000  -60.0000 102

  3 omega -111.00  -84.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -99.0000  -90.0000 27

  4 omega  -75.00  -23.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000   45.0000  -90.0000 52

  5 omega   43.00   77.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  -30.0000 34

  6 omega   37.00   67.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   90.0000 30

  7 omega   34.00   59.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000 -180.0000 25

  8 omega   30.00   63.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -60.0000 33

  9 omega   75.00  109.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000   60.0000 34

 10 omega   49.00   77.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  120.0000 28

 11 omega   50.00  122.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609 -125.0000  -30.0000 72

 12 omega   25.00  141.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -15.0000 -180.0000 116

 13 omega -119.00  -80.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -99.0000   90.0000 39

 14 omega  -12.00   68.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.3256  -57.0000   90.0000 80

 15 omega   69.00   95.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       41.3256 -125.0000  -30.0000 26

 16 omega -158.00  -97.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000 -123.0000 -111.0000 61

 17 omega   54.00   93.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000 -150.0000 39

 18 omega   85.00  154.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   30.0000 -150.0000 69

 19 omega   46.00  104.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000  120.0000 58

 20 omega   38.00   67.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   60.0000 29

 21 omega   35.00   65.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000  -90.0000 30

 22 omega   37.00   69.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000 -150.0000 32

 23 omega   30.00   68.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000   30.0000 38

 24 omega   39.00   66.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -30.0000  -60.0000 27

 25 omega   49.00  128.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000  -30.0000 79

 26 omega   47.00   77.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -45.0000    0.0000 30

 27 omega -120.00   -8.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -77.0000    0.0000 112

 28 omega -124.00  -79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -99.0000    0.0000 45

 29 omega -115.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -57.0000   30.0000 103

 30 omega -115.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -57.0000  150.0000 103

 31 omega -115.00  -12.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.3256  -57.0000  -90.0000 103

 32 omega -162.00  -49.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -30.0000 113

 33 omega -162.00  -49.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000  -90.0000 113

 34 omega -162.00  -49.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   30.0000 113

 35 omega -162.00  -49.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000 -150.0000 113

 36 omega -157.00  -53.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -61.0000  120.0000 104

 37 omega -162.00  -49.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  -77.0000   90.0000 113

 38 omega   78.00  158.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   30.0000  -90.0000 80

 39 omega   81.00  158.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   45.0000    0.0000 77

 40 omega   78.00  158.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000  150.0000 80

 41 omega   30.00  142.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -77.0000  120.0000 112

 42 omega   78.00  158.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000  -60.0000 80

 43 omega   24.00  109.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609  -94.0000    0.0000 85

 44 omega   75.00  158.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   77.0000   90.0000 83

 45 omega   78.00  158.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      108.3609   61.0000   60.0000 80

;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.043307
_diffrn_orient_matrix_UB_12      -0.1787813
_diffrn_orient_matrix_UB_13      -0.0280986
_diffrn_orient_matrix_UB_21      0.0336829
_diffrn_orient_matrix_UB_22      -0.0545687
_diffrn_orient_matrix_UB_23      0.0852481
_diffrn_orient_matrix_UB_31      -0.2092019
_diffrn_orient_matrix_UB_32      -0.0457761
_diffrn_orient_matrix_UB_33      0.0079167
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0433
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            18092
_diffrn_reflns_theta_full        71.94
_diffrn_reflns_theta_max         71.94
_diffrn_reflns_theta_min         6.73
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.66
_exptl_absorpt_correction_T_max  0.967
_exptl_absorpt_correction_T_min  0.781
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
        CrysAlisPro, Agilent Technologies,
        Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
        (compiled Feb  1 2013,16:14:44)
Analytical numeric absorption correction using a multifaceted crystal
                        model based on expressions derived by R.C. Clark & J.S.
        (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.542
_exptl_crystal_size_mid          0.4597
_exptl_crystal_size_min          0.0514
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.145
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.11(19)
_refine_ls_extinction_coef       0.0052(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     121
_refine_ls_number_reflns         1905
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0279
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0430P)^2^+0.1550P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0732
_refine_ls_wR_factor_ref         0.0737
_reflns_number_gt                1873
_reflns_number_total             1905
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja9b03679_si_003.cif
_cod_data_source_block           a20170096_rm689
_cod_original_cell_volume        974.886(16)
_cod_database_code               4127472