The Organocatalyzed Domino Michael-Aldol Reaction Revisited. Synthesis of Enantioenriched 3-Hydroxycyclohexanone Derivatives by Reaction of Enals with α,α´-Diaryl-substituted Acetone.
Pedrosa, Rafael; Adres, Jose M.; Guevara-Pulido, James O. Oswaldo; RSC Adv.  (2015) –; doi:10.1039/C5RA11215J

data_7221675
_publ_section_title
;
 The Organocatalyzed Domino Michael-Aldol Reaction Revisited. Synthesis of
 Enantioenriched 3-Hydroxycyclohexanone Derivatives by Reaction of Enals
 with \a,\a&#x00B4;-Diaryl-substituted Acetone.
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C5RA11215J
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_sum            'C24 H22 O2'
_chemical_formula_weight         342.42
_chemical_melting_point          153
_chemical_name_common
;
(2R,3R,5R,6R)-3-hydroxy-2,5,6-triphenylcyclohexanone
;
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_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_method           SHELXL-97
_audit_update_record
;
2014-10-17 deposited with the CCDC.
2015-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   5.9820(3)
_cell_length_b                   12.3210(4)
_cell_length_c                   24.7101(9)
_cell_measurement_reflns_used    5457
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.6679
_cell_measurement_theta_min      3.5745
_cell_volume                     1821.24(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 10.4757
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
  1 omega  -48.00    5.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -        0.0000   37.0000 -180.0000 53

  2 omega   30.00   88.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -        0.0000   37.0000 -180.0000 58

  3 omega  108.00  151.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -       61.0000  125.0000  -30.0000 43

  4 omega  -34.00  140.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -       61.0000  -15.0000   30.0000 174

  5 omega  118.00  144.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -       61.0000  125.0000  -90.0000 26

  6 omega  -88.00  -60.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      -70.5000  163.0000   11.0000 28

  7 omega -117.00  -92.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      -70.5000  163.0000   11.0000 25

  8 omega   90.00  117.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000 -116.0000  -42.0000 27

  9 omega   35.00   94.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  -25.0000 -120.0000 59

 10 omega   33.00   93.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  -25.0000  -60.0000 60

 11 omega   39.00   65.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000 -116.0000  -42.0000 26

 12 omega   48.00   74.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  -25.0000  -90.0000 26

 13 omega   94.00  133.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  179.0000  -30.0000 39

 14 omega  115.00  141.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000 -163.0000  -11.0000 26

 15 omega   28.00   93.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  -25.0000   90.0000 65

 16 omega  102.00  138.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  179.0000    0.0000 36

 17 omega   29.00  105.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  -50.0000   90.0000 76

 18 omega  -65.00    1.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -        0.0000  121.0000  -51.0000 66

 19 omega  -45.00  104.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000  -90.0000 149

 20 omega -155.00  -15.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      -61.0000  -45.0000  150.0000 140

 21 omega -165.00  -16.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      -61.0000  -77.0000  -90.0000 149

 22 omega   16.00  165.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -       61.0000   77.0000   30.0000 149

 23 omega   97.00  154.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -       61.0000  121.0000  128.0000 57

 24 omega -165.00  -26.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      -70.5000  -50.0000   90.0000 139

 25 omega  -90.00   10.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      -70.5000  111.0000  -60.0000 100

 26 omega   33.00  178.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000   25.0000  -90.0000 145

 27 omega  100.00  178.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  111.0000   60.0000 78

 28 omega   28.00  105.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  -50.0000  -60.0000 77

 29 omega   33.00  178.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000   25.0000  150.0000 145

 30 omega  100.00  178.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000  111.0000 -180.0000 78

 31 omega   33.00  178.00   1.0000    2.0900
omega____ theta____ kappa____ phi______ frames
    -      122.0000   25.0000   30.0000 145

;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0381882000
_diffrn_orient_matrix_UB_12      -0.1235470000
_diffrn_orient_matrix_UB_13      0.0032276000
_diffrn_orient_matrix_UB_21      -0.0239995000
_diffrn_orient_matrix_UB_22      0.0048486000
_diffrn_orient_matrix_UB_23      0.0620164000
_diffrn_orient_matrix_UB_31      -0.2535086000
_diffrn_orient_matrix_UB_32      -0.0189705000
_diffrn_orient_matrix_UB_33      -0.0053320000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0471
_diffrn_reflns_av_sigmaI/netI    0.0423
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            16324
_diffrn_reflns_theta_full        67.00
_diffrn_reflns_theta_max         76.87
_diffrn_reflns_theta_min         3.58
_exptl_absorpt_coefficient_mu    0.611
_exptl_absorpt_correction_T_max  0.967
_exptl_absorpt_correction_T_min  0.808
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            COLORLESS
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       PRISM
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.4810
_exptl_crystal_size_mid          0.2296
_exptl_crystal_size_min          0.0542
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.224
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 In order to be able to confirm the absolute structure of the molecule, 
data was collected using Cu radiation. On the basis of 1529 unmerged 
Friedel opposites (95% coverage), the Flack parameter was determined 
to be unreliable (Flack, 1983 & 2000). The absolute structure was 
confirmed using Bayesian statistics on 1519 select Bijvoet pairs (Hooft, 
Straver & Spek, 2008). The Hooft y parameter was determined to be 
-0.24(14). This supports the given absolute configuration.
;
_refine_ls_abs_structure_Flack   0.1(6)
_refine_ls_extinction_coef       0.0080(10)
_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   1.152
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         3727
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.152
_refine_ls_R_factor_all          0.1011
_refine_ls_R_factor_gt           0.0592
_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^)+(0.0979P)^2^+0.4416P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1509
_refine_ls_wR_factor_ref         0.2158
_reflns_number_gt                2490
_reflns_number_total             3727
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5ra11215j2.cif
_cod_data_source_block           J381
_cod_original_cell_volume        1821.25(13)
_cod_database_code               7221675
_refine_ls_abs_structure_hooft   -0.24(14)