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Volumn 11, Issue 9, 2009, Pages 1903-1906

Bidirectional metalation of hydrobenzoin: Direct access to new chiral ligands and auxiliaries

Author keywords

[No Author keywords available]

Indexed keywords

BENZOIN; DRUG DERIVATIVE; HYDROBENZOIN; LIGAND;

EID: 65549137614     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol900323u     Document Type: Article
Times cited : (17)

References (51)
  • 7
    • 85026862495 scopus 로고    scopus 로고
    • For a 100 g scale synthesis of (R, R)-1 from benzoin, see: Ikariya, T.; Hashiguchi, S.; Murata, K.; Noyori, R. Org. Synth. 2005, 82, 10.
    • For a 100 g scale synthesis of (R, R)-1 from benzoin, see: Ikariya, T.; Hashiguchi, S.; Murata, K.; Noyori, R. Org. Synth. 2005, 82, 10.
  • 8
    • 0001462791 scopus 로고    scopus 로고
    • For a 1 kg scale synthesis of (R,R)-1 from trans-stilbene, see: Wang, Z.-M.; Sharpless, K. B. J. Org. Chem. 1994, 59, 8302.
    • For a 1 kg scale synthesis of (R,R)-1 from trans-stilbene, see: Wang, Z.-M.; Sharpless, K. B. J. Org. Chem. 1994, 59, 8302.
  • 9
    • 66149100881 scopus 로고    scopus 로고
    • Current Aldrich prices for (R,R)-1: $2.11(CDN)/mmol. For comparison purposes the price of (R)-BINOL is $16.35(CDN)/mmol.
    • Current Aldrich prices for (R,R)-1: $2.11(CDN)/mmol. For comparison purposes the price of (R)-BINOL is $16.35(CDN)/mmol.
  • 17
    • 33744791834 scopus 로고    scopus 로고
    • For examples of chiral phosphepines and thiepines that incorporate hydrobenzoin, see: (a) Wyatt, P, Hudson, A, Charmant, J, Orpen, A. G, Phetmung, H. Org. Biomol. Chem. 2006, 4, 2218
    • For examples of chiral phosphepines and thiepines that incorporate hydrobenzoin, see: (a) Wyatt, P.; Hudson, A.; Charmant, J.; Orpen, A. G.; Phetmung, H. Org. Biomol. Chem. 2006, 4, 2218.
  • 25
    • 66149158460 scopus 로고    scopus 로고
    • For the synthesis of ortho-substituted hydrobenzoin derivatives, see refs 5f, 6a, 6b, 7a, and 7d
    • For the synthesis of ortho-substituted hydrobenzoin derivatives, see refs 5f, 6a, 6b, 7a, and 7d.
  • 26
    • 66149090695 scopus 로고    scopus 로고
    • The synthesis of ortho-functionalized hydrobenzoins typically involves McMurry coupling of an ortho-substituted benzaldehdye, followed by I2-catalyzed isomerization of the resulting stilbene and Sharpless asymmetric dihydroxylation. For examples where Sharpless asymmetric dihydroxylation of ortho-functionalized trans-stilbenes fails to provide the desired diol, see ref 7a
    • 2-catalyzed isomerization of the resulting stilbene and Sharpless asymmetric dihydroxylation. For examples where Sharpless asymmetric dihydroxylation of ortho-functionalized trans-stilbenes fails to provide the desired diol, see ref 7a.
  • 27
    • 66149143092 scopus 로고    scopus 로고
    • For complications associated with the optical enrichment of hydrobenzoin derivatives by crystallization, see ref 7d
    • For complications associated with the optical enrichment of hydrobenzoin derivatives by crystallization, see ref 7d.
  • 30
    • 66149139761 scopus 로고    scopus 로고
    • For examples of ortho-metalation reactions involving a benzyl alcohol or a-methylbenzyl alcohol, see
    • For examples of ortho-metalation reactions involving a benzyl alcohol or a-methylbenzyl alcohol, see:
  • 35
    • 66149092235 scopus 로고    scopus 로고
    • For a conceptually related but less direct approach to functionalized hydrobenzoins, see refs 6a and 6b
    • For a conceptually related but less direct approach to functionalized hydrobenzoins, see refs 6a and 6b.
  • 36
    • 0033570258 scopus 로고    scopus 로고
    • While it is unlikely that any epimerization of (R,R)-hydrobenzoin could occur during this process, the optical purity of (R,R)-hydrobenzoin recovered from the treatment of the tetraanion 10 with H2O was confirmed by chiral GC analysis. In addition, the 1H NMR spectra of the crude product contained none of the corresponding meso-hydrobenzoin, which can be differentiated from dl-hydrobenzoin by the chemical shift of the benzyl protons. 1H NMR (CDCl3) δ: 4.72 ppm (dl-hydrobenzoin, 4.80 ppm meso- hydrobenzoin, Periasamy, M, Srinivas, G, Karunakar, G. V, Bharathi, P. Tetrahedron Lett. 1999, 40, 7577
    • 3) δ: 4.72 ppm (dl-hydrobenzoin); 4.80 ppm (meso- hydrobenzoin). Periasamy, M.; Srinivas, G.; Karunakar, G. V.; Bharathi, P. Tetrahedron Lett. 1999, 40, 7577.
  • 42
    • 66149094616 scopus 로고    scopus 로고
    • Repetition of this reaction with 4 or 5 equiv of n-BuLi (reflux, 16 h) provided 14 in 19% or 34% isolated yield, respectively.
    • Repetition of this reaction with 4 or 5 equiv of n-BuLi (reflux, 16 h) provided 14 in 19% or 34% isolated yield, respectively.
  • 43
    • 66149122189 scopus 로고    scopus 로고
    • Examples of electrophiles that proved incompatible with 10 and/ or provided the desired product in very low yield (<10%) include benzaldehyde, acetone, acetaldehyde, diethylcarbonate, valeraldehyde, tri- methylsilyl chloride, cyclohexanal, crotonaldehyde, paraformaldehyde, formaldehyde, dimethylformamide, and benzylbromide.
    • Examples of electrophiles that proved incompatible with 10 and/ or provided the desired product in very low yield (<10%) include benzaldehyde, acetone, acetaldehyde, diethylcarbonate, valeraldehyde, tri- methylsilyl chloride, cyclohexanal, crotonaldehyde, paraformaldehyde, formaldehyde, dimethylformamide, and benzylbromide.
  • 44
    • 66149085210 scopus 로고    scopus 로고
    • The acetonide 19 was prepared in >97% yield by treating a solution of 14 in dimethoxypropane with a catalytic amount of HCl.
    • The acetonide 19 was prepared in >97% yield by treating a solution of 14 in dimethoxypropane with a catalytic amount of HCl.
  • 45
    • 0035982921 scopus 로고    scopus 로고
    • Attempts to directly couple the diol 14 with aryl boronic acids resulted primarily in the formation of cM-4b,9b-dihydrobenzofuro[3,2- ftjbenzofuran. For an unrelated synthesis of this substance, see: Masutani, K.; Irie, R.; Katsuki, T. Chem. Lett. 2002,36.
    • Attempts to directly couple the diol 14 with aryl boronic acids resulted primarily in the formation of cM-4b,9b-dihydrobenzofuro[3,2- ftjbenzofuran. For an unrelated synthesis of this substance, see: Masutani, K.; Irie, R.; Katsuki, T. Chem. Lett. 2002,36.
  • 46
    • 29844433863 scopus 로고    scopus 로고
    • Attempts to effect the cross-coupling of 19 with pyridine W-oxide following the procedure reported in Campeau, L.-C.; Rousseaux, S.; Fagnou, K. J. Am. Chem. Soc. 2005, 127, 18020 led predominantly to the formation of the acetonide of dihydro-phenanthrenediol.
    • Attempts to effect the cross-coupling of 19 with pyridine W-oxide following the procedure reported in Campeau, L.-C.; Rousseaux, S.; Fagnou, K. J. Am. Chem. Soc. 2005, 127, 18020 led predominantly to the formation of the acetonide of dihydro-phenanthrenediol.
  • 47
    • 0001048218 scopus 로고    scopus 로고
    • -1 for the B-O stretching modes in 3-methyl-2,1-benzoxaborol, we have tentatively assigned the structure for 17 as shown in Scheme 2. See: Dale, W. J.; Rush, J. E. J. Org. Chem. 1962, 27, 2598.
    • -1 for the B-O stretching modes in 3-methyl-2,1-benzoxaborol, we have tentatively assigned the structure for 17 as shown in Scheme 2. See: Dale, W. J.; Rush, J. E. J. Org. Chem. 1962, 27, 2598.
  • 49
    • 66149086882 scopus 로고    scopus 로고
    • 3, EtOH, DME, reflux) provided the cyclooctenyl precursor to 6 in 17% isolated yield.
    • 3, EtOH, DME, reflux) provided the cyclooctenyl precursor to 6 in 17% isolated yield.
  • 51
    • 0030058386 scopus 로고    scopus 로고
    • The acetonide of 24 has been synthesized in 6% overall yield following a six-step sequence of reactions. See: Yamamoto, H.; Kobayashi, S.; Kanemasa, S. Tetrahedron Asymmetry 1996, 7, 149.
    • The acetonide of 24 has been synthesized in 6% overall yield following a six-step sequence of reactions. See: Yamamoto, H.; Kobayashi, S.; Kanemasa, S. Tetrahedron Asymmetry 1996, 7, 149.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.