Allylic Substitution of 4-Cyclopentene-1,3-diol
Monoacetate with Copper Reagents Derived from Functionalized Aryl
Grignard Reagents

Yuichi Kobayashi; Yukio Tani; Kenya Nakata; Yuki Kaneko

doi:10.1055/s-0029-1219170

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 2010(2): 325-328
DOI: 10.1055/s-0029-1219170

CLUSTER

Allylic Substitution of 4-Cyclopentene-1,3-diol Monoacetate with Copper Reagents Derived from Functionalized Aryl Grignard Reagents

Yuichi Kobayashi*, Yukio Tani, Kenya Nakata, Yuki Kaneko
Department of Biomolecular Engineering, Tokyo Institute of Technology, B52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan
Fax: +81(45)9245789; e-Mail: ykobayas@bio.titech.ac.jp;

Further Information

Publication History

Received 6 October 2009
Publication Date:
04 January 2010 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Grignard reagents derived from IC₆H₄R (R = CO₂Et, CN, CH₂OAc, CH₂OPiv, I) and i-PrMgCl were subjected to CuCN-catalyzed allylic substitution of the monoacetate at 0 ˚C for one hour to furnish the anti-S_N2′ products regio- and stereoselectively. The ester group at the ortho-position did not affect the substitution.

Key words

allylic substitution - copper - esters - Grignard reagent - cross-coupling

References and Notes

1a Nakata K. Kiyotsuka Y. Kitazume T. Kobayashi Y. Org. Lett. 2008, 10: 1345

Google Scholar
1b Acharya HP. Miyoshi K. Kobayashi Y. Org. Lett. 2007, 9: 3535

Google Scholar
1c Nakata K. Kobayashi Y. Org. Lett. 2005, 7: 1319

Google Scholar
1d Kobayashi Y. Nakata K. Ainai T. Org. Lett. 2005, 7: 183

Google Scholar
1e Ainai T. Ito M. Kobayashi Y. Tetrahedron Lett. 2003, 44: 3983

Google Scholar
1f Kobayashi Y. Curr. Org. Chem. 2003, 7: 133

Google Scholar
1g Matsuumi M. Ito M. Kobayashi Y. Synlett 2002, 1508

Google Scholar
1h Ito M. Matsuumi M. Murugesh MG. Kobayashi Y. J. Org. Chem. 2001, 66: 5881

Google Scholar
2 Hattori H. Abbas AA. Kobayashi Y. Chem. Commun. 2004, 884

Crossref Google Scholar
3 Kobayashi Y. Murugesh MG. Nakano M. Takahisa E. Usmani SB. Ainai T. J. Org. Chem. 2002, 67: 7110

Crossref PubMed Google Scholar
4a Sugai T. Mori K. Synthesis 1988, 19

Google Scholar
4b Laumen K. Schneider M. Tetrahedron Lett. 1984, 25: 5875

Google Scholar
4c Wang Y.-F. Chen C.-S. Girdaukas G. Sih CJ. J. Am. Chem. Soc. 1984, 106: 3695

Google Scholar
5 Prostaglandins, see: Acharya HP. Kobayashi Y. Tetrahedron 2006, 62: 3329

Crossref Google Scholar
Isoprostanes, see:
6a Acharya HP. Kobayashi Y. Tetrahedron Lett. 2005, 46: 8435

Google Scholar
6b Acharya HP. Kobayashi Y. Angew. Chem. Int. Ed. 2005, 44: 3481

Google Scholar
Linolenic metabolites, see:
7a Ogawa N. Kobayashi Y. Tetrahedron Lett. 2008, 49: 7124

Google Scholar
7b Nonaka H. Wang Y.-G. Kobayashi Y. Tetrahedron Lett. 2007, 48: 1745

Google Scholar
7c Yagi K. Nonaka H. Acharya HP. Furukawa K. Ainai T. Kobayashi Y. Tetrahedron 2006, 62: 4933

Google Scholar
7d Kobayashi Y. Yagi K. Ainai T. Synlett 2004, 2582

Google Scholar
7e Ainai T. Matsuumi M. Kobayashi Y. J. Org. Chem. 2003, 68: 7825

Google Scholar
Others:
8a Hyodo T. Kiyotsuka Y. Kobayashi Y. Org. Lett. 2009, 11: 1103

Google Scholar
8b Isemori Y. Kobayashi Y. Synlett 2004, 1941

Google Scholar
8c Tokoro Y. Kobayashi Y. Chem. Commun. 1999, 807

Google Scholar
8d Kobayashi Y. Watatani K. Kikori Y. Mizojiri R. Tetrahedron Lett. 1996, 37: 6125

Google Scholar
Quinine and quinidine, see:
9a Igarashi J. Kobayashi Y. Tetrahedron Lett. 2005, 46: 6381

Google Scholar
9b Igarashi J. Ishiwata H. Kobayashi Y. Tetrahedron Lett. 2004, 45: 8065

Google Scholar
9c Igarashi J. Katsukawa M. Wang Y.-G. Acharya HP. Kobayashi Y. Tetrahedron Lett. 2004, 45: 3783

Google Scholar
10a Knochel P. Dohle W. Gommermann N. Kneisel FF. Kopp F. Korn T. Sapountzis I. Vu VA. Angew. Chem. Int. Ed. 2003, 42: 4302

Google Scholar
10b Varchi G. Ricci A. Cahiez G. Knochel P. Tetrahedron 2000, 56: 2727

Google Scholar
10c Sapountzis I. Lin W. Kofink CC. Despotopoulou C. Knochel P. Angew. Chem. Int. Ed. 2005, 44: 1654

Google Scholar

11

The ^¹H NMR spectra of 2a and 3a were consistent with those synthesized previously by us.^³

12

The spectral data of the products. Signs accompanying the chemical shifts of carbons indicate the results of APT experiments [Attached Proton Test: + (for C and CH₂) and - (for CH and CH₃)]. 2b: IR (neat): 3406, 1715, 1279, 1104, 1023 cm^-¹; ^¹H NMR (300 MHz, CDCl₃): δ = 1.38 (t, J = 7 Hz, 3 H), 1.70 (br s, 1 H), 2.09 (ddd, J = 14, 7, 6 Hz, 1 H), 2.31 (ddd, J = 14, 8, 2.5 Hz, 1 H), 4.16-4.24 (m, 1 H), 4.36 (q, J = 7 Hz, 2 H), 5.03-5.10 (m, 1 H), 6.04 (dd, J = 6, 2 Hz, 1 H), 6.08 (dt, J = 6, 2 Hz, 1 H), 7.19 (d, J = 8 Hz, 1 H), 7.96 (d, J = 8 Hz, 1 H); ^¹³C NMR (75 MHz, CDCl₃): δ = 14.4
(-), 44.0 (+), 50.0 (-), 60.9 (+), 77.4 (-), 127.1 (-), 128.8
(+), 130.0 (-), 134.8 (-), 138.4 (-), 150.2 (+), 166.6 (+). 3b: ^¹H NMR (300 MHz, CDCl₃): δ = 1.39 (t, J = 7 Hz, 3 H), 2.02 (br s, 1 H), 2.40 (dm, J = 17 Hz, 1 H), 2.82 (ddq, J = 17, 7, 2 Hz, 1 H), 3.81-3.86 (m, 1 H), 4.28 (dt, J = 7, 4 Hz, 1 H), 4.36 (q, J = 7 Hz, 2 H), 5.77 (dq, J = 6, 2.5 Hz, 1 H), 5.94 (dq, J = 6, 2 Hz, 1 H), 7.25 (d, J = 8 Hz, 1 H), 7.98 (d, J = 8 Hz, 1 H). 2c: IR (neat): 3410, 1718, 1285 cm^-¹; ^¹H NMR (300 MHz, CDCl₃): δ = 1.39 (t, J = 7 Hz, 3 H), 2.09 (ddd, J = 14, 7, 5 Hz, 1 H), 2.24 (br s, 1 H), 2.32 (ddd, J = 14, 8, 2.5 Hz, 1 H), 4.17-4.25 (m, 1 H), 4.37 (q, J = 7 Hz, 2 H), 5.04-5.11 (m, 1 H), 6.03 (dd, J = 5.5, 2 Hz, 1 H), 6.07 (dd, J = 5.5, 1.5 Hz, 1 H), 7.27-7.39 (m, 2 H), 7.81 (s, 1 H), 7.88 (d, J = 7 Hz, 1 H); ^¹³C NMR (75 MHz, CDCl₃): δ = 14.3 (-), 43.9 (+), 49.8 (-), 61.0 (+), 77.2 (-), 127.6 (-), 128.2 (+), 128.6 (-), 130.7 (+), 131.6 (-), 134.7 (-), 138.4 (-), 145.2 (-), 166.7 (+). 3c: ^¹H NMR (300 MHz, CDCl₃): δ = 1.40 (t, J = 7 Hz, 3 H), 1.94 (br s, 1 H), 2.40 (d of sext, J = 17, 2 Hz, 1 H), 2.83 (ddq, J = 17, 7, 2 Hz, 1 H), 3.81-3.86 (m, 1 H), 4.30 (dq, J = 7, 4 Hz, 1 H), 4.37 (q, J = 7 Hz, 2 H), 5.78 (dq, J = 6, 2 Hz, 1 H), 5.94 (dq, J = 6, 2 Hz, 1 H), 7.36-7.40 (m, 2 H), 7.87 (s, 1 H), 7.89-7.94 (m, 1 H). 2d: IR (neat): 3389, 1716, 1269, 755 cm^-¹; ^¹H NMR (300 MHz, CDCl₃): δ = 1.39 (t, J = 7 Hz, 3 H), 2.04 (ddd, J = 14, 7, 6 Hz, 1 H), 2.19 (br s, 1 H), 2.42 (ddd, J = 14, 8, 2.5 Hz, 1 H), 4.37 (q, J = 7 Hz, 2 H), 4.87-4.95 (m, 1 H), 4.97-5.05 (m, 1 H), 6.01 (dd, J = 5.5, 1.5 Hz, 1 H), 6.06 (dt, J = 5.5, 2 Hz, 1 H), 7.15 (d, J = 7.5 Hz, 1 H), 7.24 (t, J = 7.5 Hz, 1 H), 7.40 (t, J = 7.5 Hz, 1 H), 7.81 (d, J = 7.5 Hz, 1 H); ^¹³C NMR (75 MHz, CDCl₃): δ = 14.3 (-), 44.1 (+), 46.6 (-), 61.1 (+), 77.3 (-), 126.1 (-), 127.0 (-), 130.1 (-), 130.2 (+), 132.0 (-), 134.7 (+), 138.5 (-), 145.9 (-), 168.0 (+). 3d: ^¹H NMR (300 MHz, CDCl₃): δ = 1.42 (t, J = 7 Hz, 3 H), 2.43 (dm, J = 17 Hz, 1 H), 2.76 (ddq, J = 17, 7, 2 Hz, 1 H), 4.01 (br s, 1 H), 4.18-4.25 (m, 1 H), 4.32-4.37 (m, 1 H), 4.40 (q, J = 7 Hz, 2 H), 5.68 (dq, J = 6, 2 Hz, 1 H), 6.01 (dq, J = 6, 2 Hz, 1 H), 7.22 (d, J = 7.5 Hz, 1 H), 7.29 (t, J = 7.5 Hz, 1 H), 7.45 (t, J = 7.5 Hz, 1 H), 7.92 (d, J = 7.5 Hz, 1 H). 2e: IR (neat): 3303, 2227, 1606, 1026 cm^-¹; ^¹H NMR (300 MHz, CDCl₃): δ = 2.00-2.11 (m, 1 H), 2.22 (br s, 1 H), 2.32 (ddd, J = 14, 8, 3 Hz, 1 H), 4.17-4.25 (m, 1 H), 5.03-5.10 (m, 1 H), 6.01 (dm, J = 6 Hz, 1 H), 6.10 (dt, J = 6, 2 Hz, 1 H), 7.24 (d, J = 8.5 Hz, 2 H), 7.58 (t, J = 8.5 Hz, 2 H); ^¹³C NMR (75 MHz, CDCl₃): δ = 43.7 (+), 50.0 (-), 77.0 (-), 110.1 (+), 119.0 (+), 127.9 (-), 132.4 (-), 135.4 (-), 137.4 (+), 150.6 (+). 3e: ^¹H NMR (300 MHz, CDCl₃): δ = 1.92 (br s, 1 H), 2.42 (d of sext., J = 17, 2 Hz, 1 H), 2.82 (dddt, J = 17, 7, 1.8, 2.1 Hz, 1 H), 3.81-3.87 (m, 1 H), 4.21-4.31 (m, 1 H), 5.75 (dq, J = 6, 2 Hz, 1 H), 5.97 (dq, J = 6, 2.5 Hz, 1 H), 7.30 (d, J = 8.5 Hz, 2 H), 7.60 (t, J = 8.5 Hz, 2 H). 2f: IR (neat): 3371, 2229, 1028 cm^-¹; ^¹H NMR (300 MHz, CDCl₃): δ = 1.98 (br s, 1 H), 2.05 (ddd, J = 14, 7, 6 Hz, 1 H), 2.32 (ddd, J = 14, 8, 3 Hz, 1 H), 4.14-4.23 (m, 1 H), 5.03-5.11 (m, 1 H), 6.00 (dm, J = 5.5 Hz, 1 H), 6.11 (dt, J = 5.5, 2 Hz, 1 H), 7.35-7.53 (m, 4 H); ^¹³C NMR (75 MHz, CDCl₃): δ = 43.9 (+), 49.6 (-), 77.1 (-), 112.6 (+), 119.0 (+), 129.4
(-), 130.2 (-), 130.7 (-), 131.8 (-), 135.4 (-), 137.6 (+), 146.4 (+). 3f: ^¹H NMR (300 MHz, CDCl₃): δ = 1.91 (br s, 1 H), 2.41 (d of sext., J = 17, 2 Hz, 1 H), 2.83 (ddm, J = 17, 7 Hz, 1 H), 3.79-3.84 (m, 1 H), 4.21-4.30 (m, 1 H), 5.75 (dq, J = 6, 2 Hz, 1 H), 5.97 (dq, J = 6, 2 Hz, 1 H), 7.38-7.56 (m, 4 H). TBS ether of 2g: IR (neat): 1742, 1227, 1051, 836
cm^-¹; ^¹H NMR (300 MHz, CDCl₃): δ = 0.09 (s, 6 H), 0.91 (s, 9 H), 2.00-2.13 (m, 1 H), 2.09 (s, 3 H), 2.23 (ddd, J = 14, 8, 3.5 Hz, 1 H), 4.09-4.17 (m, 1 H), 5.07 (s, 2 H), 5.05-5.10 (m, 1 H), 5.89-5.97 (m, 2 H), 7.13 (d, J = 8 Hz, 2 H), 7.28 (d, J = 8 Hz, 2 H); ^¹³C NMR (75 MHz, CDCl₃): δ = -4.5 (-), 18.4 (+), 21.1 (-), 26.0 (-), 44.2 (+), 49.9 (-), 66.2 (+), 77.8 (-), 127.4 (-), 128.7 (-), 133.8 (-), 134.8 (+), 137.3 (-), 146.7 (+), 171.0 (+). 2h: IR (neat): 3374, 1729, 1282, 1151 cm^-¹; ^¹H NMR (300 MHz, CDCl₃): δ = 1.22 (s, 9 H), 1.60 (br s, 1 H), 2.09 (ddd, J = 14, 7, 5 Hz, 1 H), 2.29 (ddd, J = 14, 9, 3 Hz, 1 H), 4.12-4.19 (m, 1 H), 5.03-5.08 (m, 1 H), 5.07 (s, 2 H), 6.04 (s, 2 H), 7.12 (d, J = 8 Hz, 2 H), 7.26 (d, J = 8 Hz, 2 H); ^¹³C NMR (75 MHz, CDCl₃): δ = 27.2 (-), 38.8 (+), 44.0 (+), 49.7 (-), 65.9 (+), 77.4 (-), 127.2 (-), 128.0 (-), 134.2
(-), 134.5 (+), 138.8 (-), 144.7 (+), 178.5 (+). 3h: ^¹H NMR (300 MHz, CDCl₃): δ = 1.22 (s, 9 H), 1.84 (br s, 1 H), 2.38 (d of sext, J = 17, 2 Hz, 1 H), 2.81 (ddm, J = 17, 7 Hz, 1 H), 3.74-3.80 (m, 1 H), 4.24-4.32 (m, 1 H), 5.08 (s, 2 H), 5.77 (dq, J = 6, 2 Hz, 1 H), 5.91 (dq, J = 6, 2 Hz, 1 H), 7.18 (d, J = 8 Hz, 2 H), 7.28 (d, J = 8 Hz, 2 H).

13

The stereoisomer 5b was synthesized from 2b in 88% yield by using the Mitsunobu inversion (AcOH, PPh₃, DIAD, toluene, -78 ˚C, 5 h) followed by transesterification of the resulting ester with EtOH [NaH (1.4 equiv), EtOH, 0 ˚C, 4 h]. The cis-configuration of the substituents on the cyclo-pentane ring was determined by the large difference in the chemical shifts between the two hydrogens of the methylene unit (Δδ = 1.3 ppm; cf. Δδ of 2b = 0.2 ppm). The ^¹H NMR of 5b (300 MHz, CDCl₃): δ = 1.39 (t, J = 7 Hz, 3 H), 1.53-1.73 (m, 2 H), 2.88 (ddd, J = 16, 8.5, 7.5 Hz, 1 H), 3.85 (tm, J = 6 Hz, 1 H), 4.37 (q, J = 7 Hz, 2 H), 4.90-5.03 (m, 1 H), 5.95 (ddd, J = 5.5, 2, 1.5 Hz, 1 H), 6.02 (dt, J = 5.5, 2 Hz, 1 H), 7.30 (d, J = 8.5 Hz, 1 H), 7.99 (d, J = 8.5 Hz, 1 H).

14

To a solution of iodobenzoate 4b (0.15 mL, 0.902 mmol) in THF (2.5 mL) was added i-PrMgCl (1.41 mL, 0.70 M in THF, 0.987 mmol) at -30 ˚C, dropwise. The solution was stirred at -30 ˚C for 15 min, then CuCN (8.1 mg, 0.090 mmol) was added. After 20 min at 0 ˚C a solution of the racemic monoacetate 1 (42.5 mg, 0.299 mmol) in THF (1.5 mL) was added. The reaction mixture was stirred at 0 ˚C for 1 h and diluted with saturated NH₄Cl. The resulting mixture was extracted with EtOAc (3×) to afford 3b (62.5 mg) in 90% yield.