Enantioselective Synthesis of 4H-Pyran via Amine-Catalyzed Formal (3 + 3) Annulation of δ-Acetoxy Allenoate.
Zhou, Weiping; Ni, Chunjie; Chen, Jiangfei; Wang, Dong; Tong, Xiaofeng; Organic letters 19 (2017) 1890–1893; doi:10.1021/acs.orglett.7b00658

data_1545955
_publ_section_title
;
 Enantioselective Synthesis of 4H-Pyran via Amine-Catalyzed Formal (3 + 3)
 Annulation of \d-Acetoxy Allenoate.
;
_journal_issue                   7
_journal_name_full               'Organic letters'
_journal_page_first              1890
_journal_page_last               1893
_journal_paper_doi               10.1021/acs.orglett.7b00658
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C22 H22 O6'
_chemical_formula_sum            'C22 H22 O6'
_chemical_formula_weight         382.39
_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     dual
_audit_creation_date             2017-01-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.837(9)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.521(3)
_cell_length_b                   17.785(8)
_cell_length_c                   9.852(5)
_cell_measurement_reflns_used    1098
_cell_measurement_temperature    296
_cell_measurement_theta_max      19.210
_cell_measurement_theta_min      2.290
_cell_volume                     966.9(8)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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      296
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0670
_diffrn_reflns_av_unetI/netI     0.1181
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8975
_diffrn_reflns_point_group_measured_fraction_full 0.901
_diffrn_reflns_point_group_measured_fraction_max 0.848
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.426
_diffrn_reflns_theta_min         2.068
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6224
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1092 before and 0.0452 after correction.
The Ratio of minimum to maximum transmission is 0.8344.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       prism
_exptl_crystal_F_000             404
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 551 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.927
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         4551
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.927
_refine_ls_R_factor_all          0.1601
_refine_ls_R_factor_gt           0.0592
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0645P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1217
_refine_ls_wR_factor_ref         0.1545
_reflns_Friedel_coverage         0.661
_reflns_Friedel_fraction_full    0.795
_reflns_Friedel_fraction_max     0.697
_reflns_number_gt                2078
_reflns_number_total             4551
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b00658_si_003.cif
_cod_data_source_block           mo_dm17016_0m
_cod_database_code               1545955
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.986
_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
2.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C10(H10), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
2.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              93589
_shelx_hkl_checksum              53414
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'