Enantioselective Syntheses of Spiroketals via a Tandem Reaction of Cu(I) -Catalyzed Cycloetherification and H-Bond-induced [4 + 2] Cyclization.
Tian, Tian; Li, Liqi; Xue, Jijun; Zhang, Jie; Li, Ying; The Journal of organic chemistry  (2015) 150407100357003–; doi:10.1021/acs.joc.5b00384

data_4030932
_publ_section_title
;
 Enantioselective Syntheses of Spiroketals via a Tandem Reaction of Cu(I)
 -Catalyzed Cycloetherification and H-Bond-induced [4 + 2] Cyclization.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              150407100357003
_journal_paper_doi               10.1021/acs.joc.5b00384
_journal_year                    2015
_chemical_formula_moiety         'C16 H14 O3'
_chemical_formula_sum            'C16 H14 O3'
_chemical_formula_weight         254.27
_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     iterative
_audit_creation_date             2013-09-25
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            28
_cell_length_a                   11.5731(4)
_cell_length_b                   20.5327(8)
_cell_length_c                   38.4094(14)
_cell_measurement_reflns_used    5377
_cell_measurement_temperature    297.1(4)
_cell_measurement_theta_max      23.1090
_cell_measurement_theta_min      3.3880
_cell_volume                     9127.1(6)
_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
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      297.1(4)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9916
_diffrn_measured_fraction_theta_max 0.8386
_diffrn_measurement_details
;
  1 omega -101.00  -75.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.2137  178.0000 -120.0000 26

  2 omega    6.00   66.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000  -60.0000 60

  3 omega   -3.00   23.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000  -30.0000 26

  4 omega   41.00   81.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000  -30.0000 40

  5 omega   58.00   99.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  178.0000 -120.0000 41
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0215006000
_diffrn_orient_matrix_UB_12      0.0312084000
_diffrn_orient_matrix_UB_13      0.0046211000
_diffrn_orient_matrix_UB_21      0.0560239000
_diffrn_orient_matrix_UB_22      -0.0093706000
_diffrn_orient_matrix_UB_23      -0.0055622000
_diffrn_orient_matrix_UB_31      -0.0124953000
_diffrn_orient_matrix_UB_32      0.0115912000
_diffrn_orient_matrix_UB_33      -0.0169656000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0831
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            28746
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.682
_diffrn_reflns_theta_min         3.160
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83964
_exptl_absorpt_correction_type   multi-scan
_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)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.295
_exptl_crystal_description       block
_exptl_crystal_F_000             3752
_exptl_crystal_size_max          0.3700
_exptl_crystal_size_mid          0.3200
_exptl_crystal_size_min          0.2500
_refine_diff_density_max         0.164
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 3080 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.1(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1205
_refine_ls_number_reflns         16821
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.1155
_refine_ls_R_factor_gt           0.0624
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0306P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1025
_refine_ls_wR_factor_ref         0.1285
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                10029
_reflns_number_total             16821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b00384_si_002.cif
_cod_data_source_block           tiantian0624
_cod_database_code               4030932
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.16
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C10(H10), C26(H26), C42(H42), C58(H58), C71(H71), C87(H87), C103(H103)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C23(H23A,H23B), C24(H24A,H24B), C39(H39A,H39B),
 C40(H40A,H40B), C55(H55A,H55B), C56(H56A,H56B), C73(H73A,H73B), C74(H74A,H74B),
  C89(H89A,H89B), C90(H90A,H90B), C105(H10A,H10B), C106(H10C,H10D)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3A), C4(H4), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15),
 C18(H18), C19(H19), C20(H20), C21(H21), C28(H28), C29(H29), C30(H30), C31(H31),
  C34(H34), C35(H35), C36(H36), C37(H37), C44(H44), C45(H45), C46(H46),
 C47(H47), C50(H50), C51(H51), C52(H52), C53(H53), C60(H60), C61(H61), C62(H62),
  C63(H63), C66(H66), C67(H67), C68(H68), C69(H69), C76(H76), C77(H77),
 C78(H78), C79(H79), C82(H82), C83(H83), C84(H84), C85(H85), C92(H92), C93(H93),
  C94(H94), C95(H95), C98(H98), C99(H99), C100(H100), C101(H101), C108(H108),
 C109(H109), C110(H110), C111(H111)
2.d Idealised tetrahedral OH refined as rotating group:
 O3(H3), O6(H6), O9(H9), O12(H12A), O15(H15A), O18(H18A), O21(H21A)
;
_shelx_res_checksum              48625
_shelx_hkl_checksum              2080