Torquoselective Olefination
of Carbonyl Compounds with Ynolates: Highly Efficient
Stereoselective Synthesis of Tetrasubstituted Alkenes

Mitsuru Shindo; Seiji Mori

doi:10.1055/s-2008-1077971

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2008(15): 2231-2243
DOI: 10.1055/s-2008-1077971

ACCOUNT

Torquoselective Olefination of Carbonyl Compounds with Ynolates: Highly Efficient Stereoselective Synthesis of Tetrasubstituted Alkenes

Mitsuru Shindo*^a, Seiji Mori^b
^a Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen, Kasuga 816-8580, Japan
Fax: +81(92)5837875; e-Mail: shindo@cm.kyushu-u.ac.jp;
^b Faculty of Science, Ibaraki University, Mito, Ibaraki 310-8512, Japan

Further Information

Publication History

Received 26 February 2008
Publication Date:
15 July 2008 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

The torquoselectivity-controlled olefination of carbonyl compounds with ynolates affording tetrasubstituted alkenes is described. The E/Z selectivity is determined in the step consisting of electrocyclic ring opening of the β-lactone enolates (oxetenes) derived from cycloaddition of ynolates with carbonyl compounds. Theoretical calculations revealed that several secondary orbital interactions are critical for the high torquoselectivity. This methodology is a novel olefination for constructing multisubstituted olefins.

1 Introduction

2 Preparation of Ynolates

3 Olefination of Aldehydes

4 Olefination of Unfunctionalized Ketones

5 Acylsilanes and Acylgermanes

5.1 Olefination of Acylsilanes

5.2 Olefination of Acylgermanes

5.3 Olefination of Acylsilanes and Acylgermanes via Stereoselective Protonation of β-Lactone Enolates, Followed by Decarboxylation

5.4 Organic Synthesis Using Multisubstituted Vinylsilanes

5.4.1 Oxidative Cleavage of C-Si Bonds

5.4.2 Reactions of Silalactones

5.4.3 Palladium-Catalyzed Cross Coupling Activated by Hypervalency

6 Heteroatom-Directed Torquoselective Olefination

7 Olefination of Esters

8 Olefination of Aldimines

9 Conclusion

Key words

electrocyclic ring opening - olefination - theoretical calculations - torquoselectivity - ynolates

References

1a Shindo M. Mori S. J. Synth. Org. Chem., Jpn. 2008, 66: 28

Google Scholar
1b Shindo M. Tetrahedron 2007, 63: 10

Google Scholar
1c Shindo M. Synthesis 2003, 2275

Google Scholar
1d Shindo M. Yakugaku Zasshi 2000, 120: 1233 ; Chem. Abstr. 2001, 134, 178117

Google Scholar
1e Shindo M. J. Synth. Org. Chem., Jpn. 2000, 58: 1155

Google Scholar
1f Shindo M. Chem. Soc. Rev. 1998, 27: 367

Google Scholar
2 Shindo M. Sato Y. Shishido K. J. Am. Chem. Soc. 1999, 121: 6507

Crossref Google Scholar
3 Shindo M. Matsumoto K. Sato Y. Shishido K. Org. Lett. 2001, 3: 2029

Crossref PubMed Google Scholar
4 Shindo M. Sato Y. Shishido K. J. Org. Chem. 2001, 66: 7818

Crossref PubMed Google Scholar
5 Shindo M. Sato Y. Shishido K. Tetrahedron Lett. 2002, 43: 5039

Crossref Google Scholar
6 Shindo M. Yoshimura Y. Hayashi M. Soejima H. Yoshikawa T. Matsumoto K. Shishido K. Org. Lett. 2007, 9: 1963

Crossref Google Scholar
For recent reviews, see:
7a Flynn AB. Ogilvie WW. Chem. Rev. 2007, 107: 4698

Google Scholar
7b Modern Carbonyl Olefination Takeda T. Wiley-VCH; Weinheim Germany: 2004.

Google Scholar
8 Pilli RA. Derreira de Oliveira MC. Nat. Prod. Rep. 2000, 17: 117

Crossref PubMed Google Scholar
9 Harper MJK. Walpole AL. Nature (London) 1966, 212: 733

Google Scholar
10 Oishi S. Miyamoto K. Niida A. Yamamoto M. Ajito K. Tamamura H. Otaka A. Kuroda Y. Asai A. Fujii N. Tetrahedron 2006, 62: 1416

Crossref Google Scholar
11 Irie M. Chem. Rev. 2000, 100: 1685

Crossref PubMed Google Scholar
12 For an example, see: Shen Y.-M. Wang B. Shi Y. Tetrahedron Lett. 2006, 47: 5455

Google Scholar
13 Shindo M. Tetrahedron Lett. 1997, 38: 4433

Crossref Google Scholar
14 Shindo M. Sato Y. Shishido K. Tetrahedron 1998, 54: 2411

Crossref Google Scholar
15 Shindo M. Matsumoto K. Shishido K. Org. Synth. 2007, 84: 11

Crossref Google Scholar
16 Shindo M. Sato Y. Koretsune R. Yoshikawa T. Matsumoto K. Itoh K. Shishido K. Chem. Pharm. Bull. 2003, 51: 477

Crossref PubMed Google Scholar
17 For a representative review, see: Yus M. Synlett 2001, 1197

Article in Thieme Connect Google Scholar
18 Shindo M. Koretsune R. Yokota W. Itoh K. Shishido K. Tetrahedron Lett. 2001, 42: 8357

Crossref Google Scholar
19 Schöllkopf U. Hoppe I. Angew. Chem., Int. Ed. Engl. 1975, 14: 76

Google Scholar
20 Shindo M. Sato Y. Shishido K. Tetrahedron Lett. 1998, 39: 4857

Crossref Google Scholar
21 Kowalski CJ. Fields WK. J. Am. Chem. Soc. 1982, 104: 321

Crossref Google Scholar
22 Shindo M. Sato Y. Yoshikawa T. Koretsune R. Shishido K. J. Org. Chem. 2004, 69: 3912

Google Scholar
23 Shindo M. Sato Y. Shishido K. J. Org. Chem. 2000, 65: 5443

Crossref PubMed Google Scholar
24 Yu H. Chan W.-T. Goddard JD. J. Am. Chem. Soc. 1990, 112: 7529

Crossref Google Scholar
25 Mulzer J. Kerkmann T. J. Am. Chem. Soc. 1980, 102: 3620

Crossref Google Scholar
26a Niwayama S. Kallel EA. Spellmeyer DC. Sheu C. Houk KN. J. Org. Chem. 1996, 61: 2813

Google Scholar
26b Dolbier WR. Koroniak H. Houk KN. Sheu C. Acc. Chem. Res. 1996, 29: 471

Google Scholar
27 Curry MJ. Stevens DR. J. Chem. Soc., Perkin Trans. 2 1980, 1391

Google Scholar
28 Dolbier WR. Koroniak H. Burton DJ. Bailey AR. Shaw GS. Hansen SW. J. Am. Chem. Soc. 1984, 106: 1871

Google Scholar
29a Kirmse W. Rondan NG. Houk KN. J. Am. Chem. Soc. 1984, 106: 7989

Google Scholar
29b Rondan NG. Houk KN. J. Am. Chem. Soc. 1985, 107: 2099

Google Scholar
30 Murakami M. Miyamoto Y. Ito Y. Angew. Chem. Int. Ed. 2001, 40: 189

Google Scholar
31 Lee PS. Zhang X. Houk KN. J. Am. Chem. Soc. 2003, 125: 5072

Crossref PubMed Google Scholar
32 van der Meer K. Mulder JJC. Theor. Chim. Acta 1975, 37: 159

Google Scholar
33 Snyder JP. J. Org. Chem. 1980, 45: 1341

Google Scholar
34 Alabugin IV. Zeidan TA. J. Am. Chem. Soc. 2002, 124: 3175

Crossref PubMed Google Scholar
35 Mori S. Shindo M. Org. Lett. 2004, 6: 3945

Crossref PubMed Google Scholar
36 Fleming I. Barbero A. Walter D. Chem. Rev. 1997, 97: 2063

Crossref PubMed Google Scholar
37 Shindo M. Matsumoto K. Mori S. Shishido K. J. Am. Chem. Soc. 2002, 124: 6840

Crossref PubMed Google Scholar
38a Murakami M. Miyamoto Y. Ito Y. J. Am. Chem. Soc. 2001, 123: 6441

Google Scholar
38b Murakami M. Hasegawa M. Igawa H. J. Org. Chem. 2004, 69: 587

Google Scholar
39a Naruse Y. Inagaki S. Chem. Lett. 2007, 36: 820

Google Scholar
39b Ikeda H. Kato T. Inagaki S. Chem. Lett. 2001, 270

Google Scholar
39c Yasui M. Naruse Y. Inagaki S. J. Org. Chem. 2004, 69: 7246

Google Scholar
40 Hasegawa M. Murakami M. J. Org. Chem. 2007, 72: 3764

Crossref PubMed Google Scholar
41 Becke AD. J. Chem. Phys. 1993, 98: 5648

Google Scholar
41b Lee C. Yang W. Parr RG. Phys. Rev. B 1988, 37: 785

Google Scholar
42 Reed AE. Curtiss LA. Weinhold F. Chem. Rev. 1988, 88: 899

Crossref Google Scholar
43 Boys SF. Quantum Theory of Atoms, Molecules, and the Solid State Lowdin PO. Academic Press; New York: 1968. p.253-262

Google Scholar
44 Shindo M. Matsumoto K. Shishido K. Tetrahedron 2007, 63: 4271

Crossref Google Scholar
45 Shindo M. Matsumoto K. Shishido K. Chem. Commun. 2005, 2477

Google Scholar
46 Crump RANC. Fleming I. Hill JHM. Reddy NL. Waterson D. J. Chem. Soc., Perkin Trans. 1 1992, 3277

Google Scholar
47 Taguchi H. Ghoroku K. Tadaki M. Tsubouchi A. Takeda T. Org. Lett. 2001, 3: 3811

Google Scholar
48 Miller RB. Reichenbach T. Tetrahedron Lett. 1974, 543

Crossref Google Scholar
49 Shindo M. Matsumoto K. Shishido K. Angew. Chem. Int. Ed. 2004, 43: 104

Crossref PubMed Google Scholar
50 Tamao K. Hayashi T. Ito Y. Organometallics 1992, 11: 2099

Crossref Google Scholar
51 Shindo M. Matsumoto K. Shishido K. Synlett 2005, 176

Article in Thieme Connect Google Scholar
52 Hatanaka Y. Hiyama T. Synlett 1991, 845

Article in Thieme Connect Google Scholar
53 Shindo M. Yoshikawa T. Itou Y. Mori S. Nishii T. Shishido K. Chem. Eur. J. 2006, 12: 524

Crossref Google Scholar
54 Shindo M. Kita T. Kumagai T. Matsumoto K. Shishido K. J. Am. Chem. Soc. 2006, 128: 1062

Crossref PubMed Google Scholar
55 Shindo M. Yaji K. Kita T. Shishido K. Synlett 2007, 1096

Article in Thieme Connect Google Scholar
56 Kai H. Iwamoto K. Chatani N. Murai S. J. Am. Chem. Soc. 1996, 118: 7634

Crossref Google Scholar
57 Shindo M. Oya S. Murakami R. Sato Y. Shishido K. Tetrahedron Lett. 2000, 41: 5947

Crossref Google Scholar