Diastereoselective Synthesis of Diquinanes and Triquinanes Bearing Vicinal Quaternary Carbon Stereocenters from Acyclic Allene-based Precursors via a Cascade Reaction.
Li, Shuang; Zhang, Pengpeng; Li, Yuanhe; Lu, Shumin; Gong, Jianxian; Yang, Zhen; Organic letters 19 (2017) 4416–4419; doi:10.1021/acs.orglett.7b01733

data_1547007
_publ_section_title
;
 Diastereoselective Synthesis of Diquinanes and Triquinanes Bearing
 Vicinal Quaternary Carbon Stereocenters from Acyclic Allene-based
 Precursors via a Cascade Reaction.
;
_journal_issue                   17
_journal_name_full               'Organic letters'
_journal_page_first              4416
_journal_page_last               4419
_journal_paper_doi               10.1021/acs.orglett.7b01733
_journal_volume                  19
_journal_year                    2017
_chemical_formula_moiety         'C13 H22 O4'
_chemical_formula_sum            'C13 H22 O4'
_chemical_formula_weight         242.30
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                75.657(5)
_cell_angle_beta                 86.929(5)
_cell_angle_gamma                87.177(4)
_cell_formula_units_Z            4
_cell_length_a                   9.8273(9)
_cell_length_b                   11.3792(11)
_cell_length_c                   11.6772(11)
_cell_measurement_reflns_used    9822
_cell_measurement_temperature    298
_cell_measurement_theta_max      61.23
_cell_measurement_theta_min      4.01
_cell_volume                     1262.4(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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      298
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            3795
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        61.428
_diffrn_reflns_theta_max         61.428
_diffrn_reflns_theta_min         3.911
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.760
_exptl_absorpt_correction_T_max  0.752
_exptl_absorpt_correction_T_min  0.628
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1323 before and 0.0568 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1317 before and 0.0620 after correction.
 The Ratio of minimum to maximum transmission is 0.84.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 38790 reflections, Rint = 0.0437
 (29121 with I > 3sig(I), Rint = 0.0407)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       needle
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.159
_refine_diff_density_rms         0.035
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         3795
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0433
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0422P)^2^+0.3710P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0961
_refine_ls_wR_factor_ref         0.1039
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3163
_reflns_number_total             3795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b01733_si_002.cif
_cod_data_source_block           cu_cxy0094_0m_4
_cod_database_code               1547007
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.663(2)
 0.337(2)
2. 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
3. Restrained distances
 C4A-C3A = C15-C14
 1.54 with sigma of 0.02
 C2A-C1A = C1-C2
 1.54 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C14) = Uanis(C3A)
Uanis(C15) = Uanis(C4A)
Uanis(C2) = Uanis(C2A)
Uanis(C1) = Uanis(C1A)
5. Others
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=1-FVAR(1)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=1-FVAR(2)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C3(H3A), C6(H6), C7(H7), C16(H16), C24(H24), C25(H25)
6.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C1(H1A,H1B), C2(H2A,H2B), C1A(H1AA,H1AB), C2A(H2AA,H2AB), C18(H18A,H18B),
 C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C26(H26A,H26B), C14(H14A,H14B),
  C15(H15A,H15B), C3A(H3AA,H3AB), C4A(H4AA,H4AB)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C23(H23A,H23B,H23C)
6.d Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4), O7(H7A), O8(H8)
;
_shelx_res_checksum              15701
_shelx_hkl_checksum              41124
_olex2_submission_special_instructions 'No special instructions were received'