Asymmetric Synthesis of Dihydrocoumarins through Chiral Phosphoric Acid Catalyzed Cycloannulation of para-Quinone Methides and Azlactones.
Zhang, Zhi-Pei; Xie, Kai-Xue; Yang, Chen; Li, Man; Li, Xin; The Journal of organic chemistry  (2017) –; doi:10.1021/acs.joc.7b02750

data_4033282
_publ_section_title
;
 Asymmetric Synthesis of Dihydrocoumarins through Chiral Phosphoric Acid
 Catalyzed Cycloannulation of para-Quinone Methides and Azlactones.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.7b02750
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C39 H43 N O4'
_chemical_formula_sum            'C39 H43 N O4'
_chemical_formula_weight         589.74
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_symmetry_space_group_name_Hall  'P 65'
_symmetry_space_group_name_H-M   'P 65'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   15.64960(10)
_cell_length_b                   15.64960(10)
_cell_length_c                   28.7595(3)
_cell_measurement_reflns_used    36762
_cell_measurement_temperature    294(2)
_cell_measurement_theta_max      78.7130
_cell_measurement_theta_min      3.1930
_cell_volume                     6099.84(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      294.15
_diffrn_detector                 PILT
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.986
_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   -115.00 -21.00   1.00    5.00    --  -35.00 -72.00-180.00   94
  2  \w    -50.00  40.00   1.00    5.00    --  -35.00  43.00 -72.00   90
  3  \w   -114.00 -21.00   1.00    5.00    --  -35.00 -44.00-180.00   93
  4  \w    -50.00  40.00   1.00    5.00    --  -35.00  43.00-144.00   90
  5  \w   -115.00 -22.00   1.00    5.00    --  -35.00 -72.00 144.00   93
  6  \w    -50.00  40.00   1.00    5.00    --  -35.00  72.00-180.00   90
  7  \w   -115.00 -25.00   1.00    5.00    --  -35.00 -44.00-108.00   90
  8  \w   -112.00 -21.00   1.00    5.00    --  -35.00 -72.00-144.00   91
  9  \w   -119.00 -29.00   1.00    5.00    --  -35.00 -15.00-108.00   90
 10  \w   -115.00 -25.00   1.00    5.00    --  -35.00 -44.00 108.00   90
 11  \w   -115.00 -24.00   1.00    5.00    --  -35.00 -72.00 -36.00   91
 12  \w   -125.00 -33.00   1.00    5.00    --  -35.00 -72.00 -72.00   92
 13  \w   -114.00 -21.00   1.00    5.00    --  -35.00 -72.00 108.00   93
 14  \w   -191.00 -96.00   1.00   20.00    -- -110.00 -72.00-108.00   95
 15  \w   -187.00 -96.00   1.00   20.00    -- -110.00 -72.00-180.00   91
 16  \w   -125.00 -32.00   1.00   20.00    -- -110.00  72.00-108.00   93
 17  \w   -187.00 -97.00   1.00   20.00    -- -110.00 -15.00-180.00   90
 18  \w   -187.00 -96.00   1.00   20.00    -- -110.00 -44.00 144.00   91
 19  \w   -187.00 -96.00   1.00   20.00    -- -110.00 -44.00-180.00   91
 20  \w   -125.00 -33.00   1.00   20.00    -- -110.00  72.00  36.00   92
 21  \w   -187.00 -97.00   1.00   20.00    -- -110.00 -44.00-144.00   90
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Xtalab P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0784970000
_diffrn_orient_matrix_UB_12      -0.0301853000
_diffrn_orient_matrix_UB_13      0.0086469000
_diffrn_orient_matrix_UB_21      -0.0814487000
_diffrn_orient_matrix_UB_22      -0.1093666000
_diffrn_orient_matrix_UB_23      0.0008313000
_diffrn_orient_matrix_UB_31      0.0115364000
_diffrn_orient_matrix_UB_32      -0.0066903000
_diffrn_orient_matrix_UB_33      -0.0528506000
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0204
_diffrn_reflns_av_unetI/netI     0.0089
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            67790
_diffrn_reflns_point_group_measured_fraction_full 0.916
_diffrn_reflns_point_group_measured_fraction_max 0.890
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.335
_diffrn_reflns_theta_min         3.261
_diffrn_source                   'rotating anode'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.484
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80339
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    0.963
_exptl_crystal_description       prism
_exptl_crystal_F_000             1896
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.196
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 2832 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(4)
_refine_ls_extinction_coef       0.0022(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         7844
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.157
_refine_ls_R_factor_all          0.0572
_refine_ls_R_factor_gt           0.0542
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1205P)^2^+0.1114P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1594
_refine_ls_wR_factor_ref         0.1636
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    0.830
_reflns_Friedel_fraction_max     0.791
_reflns_number_gt                7047
_reflns_number_total             7844
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b02750_si_002.cif
_cod_data_source_block           p20171020b_sq
_cod_original_cell_volume        6099.84(10)
_cod_database_code               4033282
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C39H43NO4
_shelx_estimated_absorpt_t_max   0.901
_shelx_estimated_absorpt_t_min   0.853
_reflns_odcompleteness_completeness 98.41
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     79.09
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C18-C15 = C18A-C15A
 1.5 with sigma of 0.01
 C19-C20 = C19-C20A
 1.5 with sigma of 0.01
 C11-C12 \\sim C11-C12A
 with sigma of 0.01
 C18-C14 \\sim C18-C16 \\sim C18A-C14A \\sim C18A-C16A
 with sigma of 0.01
 C11-C13 \\sim C11-C17 \\sim C11-C13A \\sim C11-C17A
 with sigma of 0.01
 C19-C21 \\sim C19-C25 \\sim C19-C25A \\sim C19-C21A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C12A) \\sim Ueq,
Uanis(C13A) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq,
Uanis(C16A) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C18A) \\sim Ueq,
Uanis(C20A) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C22A) \\sim Ueq,
Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C25A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C23) = Uanis(C23A)
Uanis(C14) = Uanis(C14A)
4. Others
 Sof(C12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(C16A)=
 Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=1-FVAR(1)
 Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(C16)=Sof(H16)=
 Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=FVAR(1)
 Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=1-FVAR(2)
 Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=
 Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C19(H19C,H19D)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C27(H27), C31(H31), C13(H13), C14(H14), C16(H16),
 C17(H17), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C13A(H13A),
 C14A(H14A), C16A(H16A), C17A(H17A), C21A(H21A), C22A(H22A), C23A(H23A),
 C24A(H24A), C25A(H25A)
5.d Fitted hexagon refined as free rotating group:
 C12(C13,C14,C15,C16,C17), C20(C21,C22,C23,C24,C25), C12A(C13A,C14A,C15A,C16A,
 C17A), C20A(C21A,C22A,C23A,C24A,C25A)
5.e Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C18(H18A,
 H18B,H18C), C18A(H18D,H18E,H18F)
5.f Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_res_checksum              27126
_shelx_hkl_checksum              56878
_shelx_fab_checksum              52505
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.244
_oxdiff_exptl_absorpt_empirical_full_min 0.765