Scope and Limitations of the Scandium-Catalyzed Enantioselective Addition of Chiral Allylboronates to Aldehydes

Michel Gravel; Hugo Lachance; Xiaosong Lu; Dennis G. Hall

doi:10.1055/s-2004-822359

FEATUREARTICLE

Scope and Limitations of the Scandium-Catalyzed Enantioselective Addition of Chiral Allylboronates to Aldehydes

Michel Gravel, Hugo Lachance, Xiaosong Lu, Dennis G. Hall*
Department of Chemistry, Gunning-Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
Fax: +1(780)4928231; e-Mail: dennis.hall@ualberta.ca;

Abstract

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Abstract

Scandium triflate catalyzes the addition of camphor-derived allyl-, methallyl-, and crotylboronates to aldehydes to provide homoallylic alcohols with excellent diastereo- and enantioselectivity. Aromatic, aliphatic, and propargylic aldehydes can be used successfully in this system. Additional advantages of the camphor-diol allylboronates are their ease of synthesis, their availability in both enantiomeric forms, and their stability towards silica gel chromatography. The usefulness of this methodology is further demonstrated by the gram-scale synthesis of various homoallylic alcohols of high enantiomeric excess and by the concise synthesis of the pheromone (4S)-2-methyloctan-4-ol.

1 Introduction
2 Results and Discussion
2.1 Optimization
2.2 Substrate Scope
2.3 Synthetic Applications
2.4 Mechanistic Considerations
3 Conclusion

Key words

allylations - chiral auxiliaries - crotylations - Lewis acids - scandium

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References

For reviews see:

<A NAME="RM05003SS-1A">1a</A> Denmark SE. Almstead NG. In Modern Carbonyl Chemistry Otera J. Wiley-VCH; Weinheim: 2000. Chap. 10. p.299-402

<A NAME="RM05003SS-1B">1b</A> Chemler SR. Roush WR. In Modern Carbonyl Chemistry Otera J. Wiley-VCH; Weinheim: 2000. Chap. 11. p.403-490

<A NAME="RM05003SS-2">2</A> Brown HC. Jadhav PK. J. Am. Chem. Soc. 1983, 105: 2092

<A NAME="RM05003SS-3">3</A> Short RP. Masamune S. J. Am. Chem. Soc. 1989, 111: 1892

<A NAME="RM05003SS-4">4</A> Corey EJ. Yu C.-M. Kim SS. J. Am. Chem. Soc. 1989, 111: 5495

<A NAME="RM05003SS-5">5</A> Roush WR. Walts AE. Hoong LK. J. Am. Chem. Soc. 1985, 107: 8186

<A NAME="RM05003SS-6A">6a</A> Costa AL. Piazza MG. Tagliavini E. Trombini C. Umani-Ronchi A. J. Am. Chem. Soc. 1993, 115: 7001

<A NAME="RM05003SS-6B">6b</A> Keck GE. Tarbet KH. Geraci LS. J. Am. Chem. Soc. 1993, 115: 8467

<A NAME="RM05003SS-7">7</A> Herold T. Schrott U. Hoffmann RW. Chem. Ber. 1981, 11: 359

<A NAME="RM05003SS-8">8</A> Denmark SE. Coe DM. Pratt NE. Griedel BD. J. Org. Chem. 1994, 59: 6161

<A NAME="RM05003SS-9">9</A> Kubota K. Leighton JL. Angew. Chem. Int. Ed. 2003, 42: 946

For a notable exception using silicon reagents see ref. 9.

<A NAME="RM05003SS-11">11</A> Li Y. Houk KN. J. Am. Chem. Soc. 1989, 111: 1236

<A NAME="RM05003SS-12">12</A> Brown HC. Bhat KS. J. Am. Chem. Soc. 1986, 108: 293

<A NAME="RM05003SS-13">13</A> Roush WR. Ando K. Powers DB. Palkowitz AD. Halterman RL. J. Am. Chem. Soc. 1990, 112: 6339

<A NAME="RM05003SS-14">14</A> Garcia J. Kim B. Masamune S. J. Org. Chem. 1987, 52: 4831

<A NAME="RM05003SS-15">15</A> Hoffmann RW. Ladner W. Tetrahedron Lett. 1979, 20: 4653

<A NAME="RM05003SS-16">16</A> Denmark SE. Fu J. J. Am. Chem. Soc. 2001, 123: 9488

<A NAME="RM05003SS-17">17</A> Nakajima M. Saito M. Shiro M. Hashimoto S.-i. J. Am. Chem. Soc. 1998, 120: 6419

For examples of achiral air-stable allylboron and crotylboron reagents see:

<A NAME="RM05003SS-18A">18a</A> Batey RA. Thadani AN. Smil DV. Tetrahedron Lett. 1999, 40: 4289

<A NAME="RM05003SS-18B">18b</A> Batey RA. Thadani AN. Smil DV. Lough AJ. Synthesis 2000, 990

<A NAME="RM05003SS-19">19</A> Kennedy JWJ. Hall DG. J. Am. Chem. Soc. 2002, 124: 11586

<A NAME="RM05003SS-20">20</A> Ishiyama T. Ahiko T.-A. Miyaura N. J. Am. Chem. Soc. 2002, 124: 12414

<A NAME="RM05003SS-21">21</A> Lachance H. Lu X. Gravel M. Hall DG. J. Am. Chem. Soc. 2003, 125: 10160

<A NAME="RM05003SS-22">22</A> Luithle JEA. Pietruszka J. J. Org. Chem. 2000, 65: 9194

<A NAME="RM05003SS-23">23</A> Frantz DE. Fässler R. Carreira EM. J. Am. Chem. Soc. 2000, 122: 1806 ; and references therein

<A NAME="RM05003SS-24">24</A> A method giving moderate selectivities (58% de 71% ee) with a propargylic aldehyde was reported: Marshall JA. Palovich MR. J. Org. Chem. 1998, 63: 4381

<A NAME="RM05003SS-25">25</A> A method for crotylboration of dicobalt hexacarbonyl-masked propargylic aldehydes was reported: Roush WR. Park JC. J. Org. Chem. 1990, 55: 1143

Brown’s crotylboration reagents were also used in this context but no ee was reported:

<A NAME="RM05003SS-26A">26a</A> Nicolaou KC. Murphy F. Barluenga S. Ohshima T. Wei H. Xu J. Gray DLF. Baudoin O. J. Am. Chem. Soc. 2000, 122: 3830

<A NAME="RM05003SS-26B">26b</A> Nicolaou KC. Li Y. Fylaktakidou KC. Mitchell HJ. Wei H.-X. Weyershausen B. Angew. Chem. Int. Ed. 2001, 40: 3849

<A NAME="RM05003SS-26C">26c</A> Nicolaou KC. Fylaktakidou KC. Monenschein H. Li Y. Weyershausen B. Mitchell HJ. Wei H.-X. Guntupalli P. Hepworth D. Sugita K. J. Am. Chem. Soc. 2003, 125: 15433

<A NAME="RM05003SS-27">27</A> Johnson JR. Van Campen MG. J. Am. Chem. Soc. 1938, 60: 121

<A NAME="RM05003SS-28">28</A> Perez AL. Campos Y. Chinchilla CM. Oehlschlager AC. Gries G. Gries R. Giblin-Davis RM. Castrillo G. Peña JE. Duncan RE. Gonzalez LM. Pierce HD. McDonald R. Andrade R. J. Chem. Ecol. 1997, 23: 869

<A NAME="RM05003SS-29A">29a</A> Imai T. Tamura T. Yamamuro A. Sato T. Wollmann TA. Kennedy RM. Masamune S. J. Am. Chem. Soc. 1986, 108: 7402

<A NAME="RM05003SS-29B">29b</A> Takenaka M. Takikawa H. Mori K. Liebigs Ann. 1996, 1963

<A NAME="RM05003SS-29C">29c</A> Baraldi PT. Zarbin PHG. Vieira PC. Corrêa AG. Tetrahedron: Asymmetry 2002, 13: 621

<A NAME="RM05003SS-29D">29d</A> Zarbin PHG. Arrigoni EDB. Reckziegel A. Moreira JA. Baraldi PT. Vieira PC. J. Chem. Ecol. 2003, 29: 377

<A NAME="RM05003SS-30">30</A> Rauniyar V. Hall DG. J. Am. Chem. Soc. 2004, 126: 4518

<A NAME="RM05003SS-31">31</A> Brown HC. Racherla US. Pellechia PJ. J. Org. Chem. 1990, 55: 1868

<A NAME="RM05003SS-32">32</A> Chataigner I. Lebreton J. Zammattio F. Villiéras J. Tetrahedron Lett. 1997, 38: 3719

<A NAME="RM05003SS-33">33</A> Dale JA. Dull DL. Mosher HS. J. Org. Chem. 1969, 34: 2543

<A NAME="RM05003SS-34">34</A> Kobayashi S. Nishio K. J. Org. Chem. 1994, 59: 6620

<A NAME="RM05003SS-35">35</A> Roush WR. Hoong LK. Palmer MAJ. Straub JA. Palkowitz AD. J. Org. Chem. 1990, 55: 4117

<A NAME="RM05003SS-36">36</A> Malacria M. Journet M. J. Org. Chem. 1992, 57: 3085

<A NAME="RM05003SS-37">37</A> Thadani AN. Batey RA. Org. Lett. 2002, 4: 3827

<A NAME="RM05003SS-38">38</A> McCluskey A. Muderawan IW. . Young DJ. J. Org. Chem. 2001, 66: 7811

<A NAME="RM05003SS-39">39</A> Tokuda M. Satoh S. Suginome H. J. Org. Chem. 1989, 54: 5608

<A NAME="RM05003SS-40">40</A> Chemler SR. Roush WR. J. Org. Chem. 1998, 63: 3800

<A NAME="RM05003SS-41">41</A> Wipf P. Reeves JT. Chem. Commun. 2002, 2066

<A NAME="RM05003SS-42">42</A> Iseki K. Kuroki Y. Takahashi M. Kishimoto S. Kobayashi Y. Tetrahedron 1997, 53: 3513

<A NAME="RM05003SS-43">43</A> Boeckman RK. Charette AB. Asberom T. Johnston BH. J. Am. Chem. Soc. 1991, 113: 5337

<A NAME="RM05003SS-44">44</A> Scarlato GR. DeMattei JA. Chong LS. Ogawa AK. Lin MR. Armstrong RW. J. Org. Chem. 1996, 61: 6139

<A NAME="RM05003SS-45">45</A> Ishihara K. Mouri M. Gao Q. Maruyama T. Furuta K. Yamamoto H. J. Am. Chem. Soc. 1993, 115: 11490