Catalytic Asymmetric Hydroxylative Dearomatization of 2-Naphthols: Synthesis of Lacinilene Derivatives
Zhang, Yu; Liao, Yuting; Liu, Xiaohua; Xu, Xi; Lin, Lili; Feng, Xiaoming; Chem. Sci.  (2017) –; doi:10.1039/C7SC02809A

data_1546623
_publ_section_title
;
 Catalytic Asymmetric Hydroxylative Dearomatization of 2-Naphthols:
 Synthesis of Lacinilene Derivatives
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC02809A
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H28 O3 Si'
_chemical_formula_sum            'C19 H28 O3 Si'
_chemical_formula_weight         332.50
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-03-09 deposited with the CCDC.
2017-07-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.846(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.9182(9)
_cell_length_b                   6.1752(3)
_cell_length_c                   14.8927(6)
_cell_measurement_reflns_used    8100
_cell_measurement_temperature    135
_cell_measurement_theta_max      72.1700
_cell_measurement_theta_min      4.1490
_cell_volume                     1979.71(15)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      135
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.954
_diffrn_measurement_details
;
  1 omega  -31.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -57.0000   30.0000 84

  2 omega   23.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671 -125.0000    0.0000 67

  3 omega   17.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   38.0000 -120.0000 88

  4 omega   17.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   38.0000 -180.0000 88

  5 omega  -34.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   -6.0000 -153.0000 139

  6 omega    9.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000 -150.0000 95

  7 omega   19.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   57.0000    0.0000 84

  8 omega   17.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   38.0000  150.0000 88

  9 omega   26.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -99.0000  -30.0000 43

 10 omega   19.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   57.0000   30.0000 34

 11 omega    9.00   57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000   90.0000 48

 12 omega   77.00  102.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000  150.0000 25

 13 omega   78.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   57.0000   30.0000 25

 14 omega   31.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   57.0000 -150.0000 27

 15 omega    7.00   49.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   19.0000 -180.0000 42

 16 omega    7.00   34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671  -77.0000   90.0000 27

 17 omega   17.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.1671   77.0000  150.0000 41

 18 omega   87.00  113.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  150.0000 26

 19 omega  132.00  158.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 26

 20 omega   44.00   95.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 51

 21 omega   82.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 25

 22 omega   71.00   96.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   90.0000 25

 23 omega  121.00  172.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 51

 24 omega   81.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 26

 25 omega   87.00  113.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -180.0000 26

 26 omega   91.00  116.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -180.0000 25

 27 omega   90.00  116.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   90.0000 26

 28 omega   39.00   64.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   60.0000 25

 29 omega   80.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   60.0000 27

 30 omega   94.00  121.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   60.0000 27

 31 omega   43.00  108.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 65

 32 omega  122.00  169.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 47

 33 omega   81.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 26

 34 omega   81.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 26

 35 omega   90.00  116.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   60.0000 26

 36 omega   81.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 26

 37 omega   95.00  123.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  150.0000 28

 38 omega   91.00  117.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   60.0000 26

 39 omega   90.00  117.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 27

 40 omega   91.00  118.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000    0.0000 27

 41 omega   97.00  124.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   90.0000 27

 42 omega   81.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 26

 43 omega   82.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 25

 44 omega  115.00  175.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 60

 45 omega   70.00   97.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -180.0000 27

 46 omega   90.00  117.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 27

 47 omega   87.00  113.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  120.0000 26

 48 omega  113.00  175.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 62

 49 omega   87.00  114.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   90.0000 27

 50 omega   91.00  117.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 26

 51 omega   92.00  117.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -180.0000 25

 52 omega   89.00  114.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -150.0000 25

 53 omega   81.00  107.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 26

 54 omega  120.00  174.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 54

 55 omega   73.00  100.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  120.0000 27

 56 omega   87.00  114.00   1.0000    3.2400
omega____ theta____ kappa____ phi______ frames
    -      108.0000   29.0000 -154.2492 27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0809792000
_diffrn_orient_matrix_UB_12      -0.0069772000
_diffrn_orient_matrix_UB_13      -0.0553219000
_diffrn_orient_matrix_UB_21      -0.0675319000
_diffrn_orient_matrix_UB_22      0.0167604000
_diffrn_orient_matrix_UB_23      0.0450824000
_diffrn_orient_matrix_UB_31      0.0025235000
_diffrn_orient_matrix_UB_32      0.2486926000
_diffrn_orient_matrix_UB_33      -0.0045379000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0590
_diffrn_reflns_av_unetI/netI     0.0504
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20490
_diffrn_reflns_point_group_measured_fraction_full 0.878
_diffrn_reflns_point_group_measured_fraction_max 0.831
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.969
_diffrn_reflns_theta_min         5.543
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.133
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36063
_exptl_absorpt_correction_type   multi-scan
_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)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.116
_exptl_crystal_description       plate
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.75
_exptl_crystal_size_mid          0.6
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.529
_refine_diff_density_min         -0.477
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 2055 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     431
_refine_ls_number_reflns         6769
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0608
_refine_ls_shift/su_max          0.019
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1180P)^2^+0.5720P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1649
_refine_ls_wR_factor_ref         0.1857
_reflns_Friedel_coverage         0.587
_reflns_Friedel_fraction_full    0.732
_reflns_Friedel_fraction_max     0.681
_reflns_number_gt                6165
_reflns_number_total             6769
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc02809a2.cif
_cod_data_source_block           fxm-zy-tbsoh-135k
_cod_depositor_comments
;

2019-03-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C19 H28 O3 Si)'
_cod_original_formula_sum        'C38 H56 O6 Si2'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     665.00
_cod_database_code               1546623
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. 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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C16(H16), C17(H17), C18(H18), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C31(H31A,H31B,H31C), C32(H32A,H32B,
 H32C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C1AA(H1AA,H1AB,H1AC), C0AA(H0AA,H0AB,H0AC)
2.d Idealised tetrahedral OH refined as rotating group:
 O0AA(H0AD), O3(H3)
;
_shelx_res_checksum              7172
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2017-01-10
_olex2_submission_special_instructions 'No special instructions were received'