Diastereoselective synthesis of axially chiral xylose-derived 1,3-disubstituted alkoxyallenes: scope, structure and mechanism.
Fortunato, Moustapha; Gimbert, Yves; Rousset, Elodie; Lameiras, Pedro; Martinez, Agathe; Gatard, Sylvain; Plantier-Royon, Richard; Jaroschik, Florian; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01240

data_4038646
_publ_section_title
;
 Diastereoselective synthesis of axially chiral xylose-derived
 1,3-disubstituted alkoxyallenes: scope, structure and mechanism.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01240
_journal_year                    2020
_chemical_absolute_configuration syn
_chemical_formula_moiety
'0.75(C27 H56 O5 Si3), 1(O), 0.25(C27 H55 O5 Si3)'
_chemical_formula_sum            'C27 H55.75 O6 Si3'
_chemical_formula_weight         560.73
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.000(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.8580(16)
_cell_length_b                   31.257(6)
_cell_length_c                   28.576(6)
_cell_measurement_reflns_used    2273
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      27.879
_cell_measurement_theta_min      0.407
_cell_volume                     7019(2)
_computing_cell_refinement       'XDS (Kabsch, 1993)'
_computing_data_collection       'BluIce (McPhillips, 2002)'
_computing_data_reduction        'XDS (Kabsch, 1993)'
_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      100.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'ADSC Quantum 315r'
_diffrn_measurement_method       'Phi Scan'
_diffrn_radiation_monochromator  'Silicon Double Crystal'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.710751
_diffrn_reflns_av_R_equivalents  0.0884
_diffrn_reflns_av_unetI/netI     0.1282
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            146852
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.032
_diffrn_reflns_theta_min         1.303
_diffrn_source                   'MX2 Beamline Australian Synchrotron'
_exptl_absorpt_coefficient_mu    0.168
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
XDS (Kabsch, 1993) was used for absorption correction. 
No further details are reported by XDS.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.061
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2462
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.110
_exptl_crystal_size_min          0.035
_refine_diff_density_max         1.894
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details
;
 Flack x determined using 12288 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1454
_refine_ls_number_reflns         39535
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1062
_refine_ls_R_factor_gt           0.0979
_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^)+(0.1724P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2425
_refine_ls_wR_factor_ref         0.2594
_reflns_Friedel_coverage         0.961
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                33188
_reflns_number_total             39535
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01240_si_002.cif
_cod_data_source_block           er-19mfolter-tri
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Multi-Scan' was
changed to 'multi-scan' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               4038646
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.067
_shelx_estimated_absorpt_t_min   0.012
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6370(19)
 0.3630(19)
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
3. Shared sites
{O7A, O7}
{C78A, C78}
{O17, O17A}
4. Restrained distances
 C18-C21 = C18-C19
 1.5 with sigma of 0.01
 C24-C27 = C24-C25
 1.5 with sigma of 0.01
 C27-C26 = C26-C25 = C25-C27
 2.4602 with sigma of 0.001
 C39-C41
 1.35432 with sigma of 0.005
5. Uiso/Uaniso restraints and constraints
C79 \\sim C79A \\sim C80 \\sim C80A \\sim C81 \\sim C81A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C108) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C27) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C35A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C81A) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C79A) \\sim Ueq, Uanis(C79)
\\sim Ueq, Uanis(C80A) \\sim Ueq, Uanis(C80) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O17) = Uanis(O17A)
Uanis(C87) = Uanis(C87A)
Uanis(C88) = Uanis(C88A)
Uanis(C89) = Uanis(C89A)
Uanis(C90) = Uanis(C90A)
Uanis(O7A) = Uanis(O7)
Uanis(C33A) = Uanis(C33)
Uanis(C34A) = Uanis(C34)
Uanis(C35A) = Uanis(C35)
Uanis(C36A) = Uanis(C36)
Uanis(C78A) = Uanis(C78)
Uanis(O8W) = Uanis(O10W) = Uanis(O12W) = Uanis(O7W) = Uanis(O9W) = Uanis(O14W)
= Uanis(O6W) = Uanis(O2W) = Uanis(O17W) = Uanis(O16W) = Uanis(O11W) =
Uanis(O4W) = Uanis(O5W) = Uanis(O13W) = Uanis(O18W) = Uanis(O15W) = Uanis(O1W)
= Uanis(O3W)
6. Same fragment restrains
{O7A, C33A, C34A, C35A, C36A} sigma for 1-2: 0.02, 1-3: 0.04
as
{O7, C33, C34, C35, C36}
{C78A, C79A, C80A, C81A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C78, C79, C80, C81}
{O17, C87, C88, C89, C90} sigma for 1-2: 0.02, 1-3: 0.04
as
{O17A, C87A, C88A, C89A, C90A}
7. Others
 1*[Sof(O8W)]+1*[Sof(O10W)]+3*[Sof(O7W)+Sof(O14W)+Sof(O4W)]+1*[Sof(O9W)]+1*
 [Sof(O12W)]+1*[Sof(O6W)]+1*[Sof(O2W)]+1*[Sof(O17W)]+1*[Sof(O16W)]+1*
 [Sof(O11W)]+1*[Sof(O5W)]+2*[Sof(O13W)+Sof(O15W)]+2*[Sof(O1W)+Sof(O18W)]+1*
 [Sof(O3W)]=4 with esd of 0.0001
 Sof(O7A)=Sof(H28A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(C35A)=Sof(H35A)=
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=1-FVAR(1)
 Sof(O7)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=Sof(H28)=FVAR(1)
 Sof(C78A)=Sof(C79A)=Sof(H79D)=Sof(H79E)=Sof(H79F)=Sof(C80A)=Sof(H80D)=
 Sof(H80E)=Sof(H80F)=Sof(C81A)=Sof(H81D)=Sof(H81E)=Sof(H81F)=1-FVAR(2)
 Sof(C78)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C80)=Sof(H80A)=Sof(H80B)=
 Sof(H80C)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=FVAR(2)
 Sof(O17A)=Sof(C87A)=Sof(H87A)=Sof(C88A)=Sof(C89A)=Sof(H89A)=Sof(C90A)=
 Sof(H90A)=Sof(H90B)=Sof(H90C)=1-FVAR(3)
 Sof(O17)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(C89)=Sof(H89)=Sof(C90)=Sof(H90D)=
 Sof(H90E)=Sof(H90F)=FVAR(3)
 Sof(O7W)=Sof(O14W)=Sof(O4W)=FVAR(6)
 Sof(O13W)=Sof(O15W)=FVAR(15)
 Sof(O1W)=Sof(O18W)=FVAR(16)
8.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C28(H28), C28(H28A), C29(H29), C30(H30),
 C31(H31), C55(H55), C56(H56), C57(H57), C58(H58), C83(H83), C84(H84), C85(H85)
8.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C32(H32A,H32B), C59(H59A,H59B), C86(H86A,H86B)
8.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C35(H35), C6(H6), C8(H8), C33A(H33A), C35A(H35A), C60(H60),
 C62(H62), C87A(H87A), C89A(H89A), C87(H87), C89(H89)
8.d Idealised Me refined with riding coordinates:
 C36(H36A,H36B,H36C), C15(H15A,H15B,H15C), C36A(H36D,H36E,H36F), C67(H67A,H67B,
 H67C), C90A(H90A,H90B,H90C), C90(H90D,H90E,H90F)
8.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10Y,H,HA), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C),
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,
 H54C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C68(H68A,
 H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C),
 C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,
 H76C), C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,
 H81B,H81C), C79A(H79D,H79E,H79F), C80A(H80D,H80E,H80F), C81A(H81D,H81E,H81F),
 C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C94(H94A,H94B,H94C), C95(H95A,H95B,
 H95C), C96(H96A,H96B,H96C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C),
 C100(H10A,H10B,H10C), C101(H10D,H10E,H10F), C102(H10G,H10H,H10I), C103(H10J,
 H10K,H10L), C104(H10M,H10N,H10O), C106(H10P,H10Q,H10R), C107(H10S,H10T,H10U),
 C108(H10V,H10W,H10X)
;
_shelx_res_checksum              65601
_shelx_hkl_checksum              37922
_olex2_submission_special_instructions 'No special instructions were received'