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_4038645
_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         'C26 H54 O5 Si3'
_chemical_formula_sum            'C26 H54 O5 Si3'
_chemical_formula_weight         530.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-05-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.747(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.9222(10)
_cell_length_b                   7.8099(3)
_cell_length_c                   31.9633(10)
_cell_measurement_reflns_used    9110
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      68.24
_cell_measurement_theta_min      3.02
_cell_volume                     6608.6(4)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      110.01
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_unetI/netI     0.0536
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            37670
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.350
_diffrn_reflns_theta_min         3.021
_diffrn_source                   Cu
_exptl_absorpt_coefficient_mu    1.550
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5505
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1406 before and 0.0824 after correction. The Ratio of minimum to maximum transmission is 0.7310.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.067
_exptl_crystal_description       needle
_exptl_crystal_F_000             2336
_exptl_crystal_size_max          0.318
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.678
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 4633 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.111(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     963
_refine_ls_number_reflns         12012
_refine_ls_number_restraints     343
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0436
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0430P)^2^+5.4841P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1034
_refine_ls_wR_factor_ref         0.1076
_reflns_Friedel_coverage         0.836
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                11099
_reflns_number_total             12012
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01240_si_002.cif
_cod_data_source_block           19mf02_0m
_cod_database_code               4038645
_shelx_shelxl_version_number     2018/3
_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. Uiso/Uaniso restraints and constraints
C32 \\sim C33 \\sim C34 \\sim C32A \\sim C33A \\sim C34A: within 1.9A with
sigma of 0.005 and sigma for terminal atoms of 0.01
Si6 \\sim Si6A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Si5 \\sim Si5A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Si4 \\sim Si4A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O6 \\sim O6A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O10 \\sim O10A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O9 \\sim O9A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O8 \\sim O8A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O7 \\sim O7A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C31 \\sim C31A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C30 \\sim C30A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C29 \\sim C29A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C28 \\sim C28A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C27 \\sim C27A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C47 \\sim C47A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C48 \\sim C48A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C49 \\sim C49A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C51 \\sim C51A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C50 \\sim C50A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C52 \\sim C52A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C41 \\sim C41A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C42 \\sim C42A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C43 \\sim C43A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C44 \\sim C44A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C45 \\sim C45A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C46 \\sim C46A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C36 \\sim C36A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C35 \\sim C35A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C37 \\sim C37A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C39 \\sim C40A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C38 \\sim C38A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C40 \\sim C39A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C32 \\sim C32A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C34 \\sim C34A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
C33 \\sim C33A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C31) \\sim Ueq, Uanis(C31A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C52) \\sim Ueq, Uanis(C52A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C42A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C29A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C41A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
3. Same fragment restrains
{Si4, Si5, Si6, O6, O7, O8, O9, O10, C27, C28, C29, C30, C31, C32, C33, C34,
C35, C36, C37, C38, C40, C39, C41, C42, C43, C44, C45, C46, C47, C48, C49, C50,
C51, C52} sigma for 1-2: 0.01, 1-3: 0.04
as
{Si4A, Si5A, Si6A, O6A, O7A, O8A, O9A, O10A, C27A, C28A, C29A, C30A, C31A,
C32A, C33A, C34A, C35A, C36A, C37A, C38A, C39A, C40A, C41A, C42A, C43A, C44A,
C45A, C46A, C47A, C48A, C49A, C50A, C51A, C52A}
4. Others
 Sof(Si4A)=Sof(Si5A)=Sof(Si6A)=Sof(O6A)=Sof(O7A)=Sof(O8A)=Sof(O9A)=Sof(O10A)=
 Sof(C27A)=Sof(H27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=
 Sof(H30A)=Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32C)=Sof(H32D)=
 Sof(C33A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37A)=Sof(C38A)=Sof(H38D)=
 Sof(H38E)=Sof(H38F)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40A)=
 Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=
 Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=Sof(C43A)=Sof(C44A)=Sof(H44D)=
 Sof(H44E)=Sof(H44F)=Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C46A)=
 Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=
 Sof(C48A)=Sof(H48D)=Sof(H48E)=Sof(H48F)=Sof(C49A)=Sof(C50A)=Sof(H50D)=
 Sof(H50E)=Sof(H50F)=Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52A)=
 Sof(H52D)=Sof(H52E)=Sof(H52F)=1-FVAR(1)
 Sof(Si4)=Sof(Si5)=Sof(Si6)=Sof(O6)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(O10)=Sof(C27)=
 Sof(H27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=
 Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C33)=Sof(C34)=Sof(H34)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C37)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(C44)=Sof(H44A)=
 Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(H46C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=Sof(H48A)=
 Sof(H48B)=Sof(H48C)=Sof(C49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C51)=
 Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C27(H27), C28(H28), C29(H29), C30(H30),
 C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A)
5.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C31(H31A,H31B), C32(H32A,H32B), C31A(H31C,H31D),
 C32A(H32C,H32D)
5.c Me refined with riding coordinates:
 C51(H51A,H51B,H51C), C51A(H51D,H51E,H51F)
5.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C),
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C),
 C35A(H35D,H35E,H35F), C36A(H36D,H36E,H36F), C38A(H38D,H38E,H38F), C39A(H39D,
 H39E,H39F), C40A(H40D,H40E,H40F), C41A(H41D,H41E,H41F), C42A(H42D,H42E,H42F),
 C44A(H44D,H44E,H44F), C45A(H45D,H45E,H45F), C46A(H46D,H46E,H46F), C47A(H47D,
 H47E,H47F), C48A(H48D,H48E,H48F), C50A(H50D,H50E,H50F), C52A(H52D,H52E,H52F)
5.e :
 C8(H8), C34(H34), C34A(H34A)
;
_shelx_res_checksum              20608
_shelx_hkl_checksum              78297
_olex2_submission_special_instructions 'No special instructions were received'