An organocatalytic Michael-cyclization cascade of 4-oxa-alpha,beta-unsaturated carboxylic acids with aldehydes: facile synthesis of chiral gamma-lactols and trisubstituted gamma-lactones
Jun-Bing Lin; Shi-Ming Xu; Ji-Kang Xie; Hong-Yu Li; Peng-Fei Xu; Chem.Commun. 51 (2015) 3596–; doi:10.1039/C4cc09686J

data_7116551
_publ_section_title
;
 An organocatalytic Michael-cyclization cascade of
 4-oxa-alpha,beta-unsaturated carboxylic acids with aldehydes: facile
 synthesis of chiral gamma-lactols and trisubstituted gamma-lactones
;
_journal_name_full               Chem.Commun.
_journal_page_first              3596
_journal_paper_doi               10.1039/C4cc09686J
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H17 Br O4'
_chemical_formula_sum            'C19 H16 Br O4'
_chemical_formula_weight         388.23
_chemical_name_systematic
;
?
;
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-02-27
_audit_creation_method
;
Olex2 1.2
(compiled Dec 5 2012 16:20:19, GUI svn.r4385)
;
_audit_update_record
;
2013-02-27 deposited with the CCDC.
2015-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 96.833(6)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   5.8959(3)
_cell_length_b                   11.7317(6)
_cell_length_c                   12.7300(9)
_cell_measurement_reflns_used    848
_cell_measurement_temperature    293.66(10)
_cell_measurement_theta_max      28.3836
_cell_measurement_theta_min      3.2170
_cell_volume                     874.27(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_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
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      293.66(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9979
_diffrn_measured_fraction_theta_max 0.9788
_diffrn_measurement_details
;
1 omega -10.00 17.00 1.0000 4.0000
omega____ theta____ kappa____ phi______ frames
- -19.3492 -99.0000 -30.0000 27

2 omega -35.00 52.00 1.0000 4.0000
omega____ theta____ kappa____ phi______ frames
- 22.7867 -77.0000 -180.0000 87

3 omega -29.00 83.00 1.0000 4.0000
omega____ theta____ kappa____ phi______ frames
- 22.7867 19.0000 30.0000 112
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0050908000
_diffrn_orient_matrix_UB_12      -0.0145926000
_diffrn_orient_matrix_UB_13      -0.0543085000
_diffrn_orient_matrix_UB_21      -0.0308134000
_diffrn_orient_matrix_UB_22      0.0568975000
_diffrn_orient_matrix_UB_23      -0.0141303000
_diffrn_orient_matrix_UB_31      0.1170714000
_diffrn_orient_matrix_UB_32      0.0143095000
_diffrn_orient_matrix_UB_33      0.0008627000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_unetI/netI     0.0555
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            3487
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         3.22
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.370
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54072
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
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    1.475
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             394
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.272
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.021(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         2479
_refine_ls_number_restraints     31
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0864
_refine_ls_R_factor_gt           0.0522
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0519P)^2^+0.1199P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1050
_refine_ls_wR_factor_ref         0.1240
_reflns_number_gt                1727
_reflns_number_total             2479
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c4cc09686j2.cif
_cod_data_source_block           suyu0111
_cod_database_code               7116551
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
At 1.2 times of:
H9 of C9, H10 of C10, H11 of C11, {H12A,H12B} of C12, H15 of C15, H16 of
C16, H18 of C18, H19 of C19, H8 of C8, H1 of C1, H3A of C3, H4 of C4, {H5A,
H5B} of C5, H7 of C7
At 1.5 times of:
H3 of O3
2. Uiso/Uaniso restraints and constraints
Uanis(C11) ~ Ueq, Uanis(C10) ~ Ueq, Uanis(C9) ~ Ueq, Uanis(C8) ~ Ueq, Uanis(C7) ~ Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
C1(H1), C3(H3A), C4(H4)
3.b Secondary CH2 refined with riding coordinates:
C5(H5A,H5B), C12(H12A,H12B)
3.c Aromatic/amide H refined with riding coordinates:
C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C15(H15), C16(H16), C18(H18),
C19(H19)
3.d Idealised tetrahedral OH refined as rotating group:
O3(H3)
;