Organocatalytic Asymmetric Tandem Nazarov Cyclization/Semipinacol Rearrangement: Rapid Construction of Chiral Spiro[4.4]nonane-1,6-diones.
Yang, Bin-Miao; Cai, Pei-Jun; Tu, Yong-Qiang; Yu, Zhi-Xiang; Chen, Zhi-Min; Wang, Shuang-Hu; Wang, Shao-Hua; Zhang, Fu-Min; Journal of the American Chemical Society 137 (2015) 8344–8347; doi:10.1021/jacs.5b04049

data_4123870
_publ_section_title
;
 Organocatalytic Asymmetric Tandem Nazarov Cyclization/Semipinacol
 Rearrangement: Rapid Construction of Chiral Spiro[4.4]nonane-1,6-diones.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8344
_journal_page_last               8347
_journal_paper_doi               10.1021/jacs.5b04049
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety         'C16 H17 Cl O2'
_chemical_formula_sum            'C16 H17 Cl O2'
_chemical_formula_weight         276.74
_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
_audit_creation_date             2014-05-19
_audit_creation_method
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Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6183(6)
_cell_length_b                   11.0140(5)
_cell_length_c                   10.1521(4)
_cell_measurement_reflns_used    2597
_cell_measurement_temperature    294.53(10)
_cell_measurement_theta_max      70.6100
_cell_measurement_theta_min      4.3150
_cell_volume                     1410.92(11)
_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
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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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.53(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0074818000
_diffrn_orient_matrix_UB_12      0.1308220000
_diffrn_orient_matrix_UB_13      0.0527418000
_diffrn_orient_matrix_UB_21      -0.0080837000
_diffrn_orient_matrix_UB_22      -0.0479111000
_diffrn_orient_matrix_UB_23      0.1421654000
_diffrn_orient_matrix_UB_31      0.1216627000
_diffrn_orient_matrix_UB_32      -0.0113322000
_diffrn_orient_matrix_UB_33      0.0062526000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0270
_diffrn_reflns_av_unetI/netI     0.0360
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            4625
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.225
_diffrn_reflns_theta_min         5.331
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.352
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68848
_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    1.303
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.34
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.160
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 976 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.003(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     182
_refine_ls_number_reflns         2619
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0405
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0630P)^2^+0.0851P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1070
_refine_ls_wR_factor_ref         0.1095
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                2460
_reflns_number_total             2619
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b04049_si_002.cif
_cod_data_source_block           yangbm0519_1
_cod_depositor_comments
'Adding full bibliography for 4123869--4123871.cif.'
_cod_original_cell_volume        1410.91(11)
_cod_database_code               4123870
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.19
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C8') \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Fixed Sof: H7AA(0.6) H7AB(0.6) H7BC(0.4) H7BD(0.4) H9AA(0.6) H9AB(0.6)
 H9BC(0.4) H9BD(0.4) C8(0.6) H8A(0.6) H8B(0.6) C8'(0.4) H8'A(0.4) H8'B(0.4)
4.a Ternary CH refined with riding coordinates:
 C1(H1), C3(H3)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7AA,H7AB), C7(H7BC,H7BD), C9(H9AA,H9AB), C9(H9BC,H9BD),
 C8(H8A,H8B), C8'(H8'A,H8'B)
4.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C14(H14), C15(H15)
4.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              50676
_shelx_hkl_checksum              80201