π-Allyl Palladium Complexes as Efficient and Powerful Alternative for Nucleophilic Substitution on Bicyclo[3.1.0]hexane Sulfonates: Regio-, Chemo- and Stereoselectivity

Frédéric Lecornué; Florence Charnay-Pouget; Jean Ollivier

doi:10.1055/s-2006-939716

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Synlett 2006(9): 1407-1409
DOI: 10.1055/s-2006-939716

LETTER

π-Allyl Palladium Complexes as Efficient and Powerful Alternative for Nucleophilic Substitution on Bicyclo[3.1.0]hexane Sulfonates: Regio-, Chemo- and Stereoselectivity

Frédéric Lecornué^b, Florence Charnay-Pouget^a, Jean Ollivier*^a
^a Synthèse Organique et Méthodologie, UMR 8182, Institut de Chimie Moléculaire et des Matériaux d"Orsay, Bât. 420, Université Paris-Sud, 91405 Orsay, France
Fax: +33(1)69156278; e-Mail: jollivie@icmo.u-psud.fr;
^b Synthèse et Réactivité des Substances Naturelles, Département de Chimie, SFA-UMR 6514, Université Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers, France

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Publication History

Received 14 February 2006
Publication Date:
22 May 2006 (online)

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Abstract

The preparation of cyclopropylidene bicyclo[3.1.0]hexane derivatives has been performed on both exo- and endo-bicyclo[3.1.0]hexane sulfonates, through nucleophilic substitution via π-allyl palladium complexes. While the endo- and exo-configurations do not particularly affect the selectivities of the products, on the other hand, the ‘hard’ or ‘soft’ nature of nucleophiles dramatically enhances the conservation or not of the integrity of the cyclopropane rings.

Key words

palladium - chemoselectivity - complexes - nucleophilic additions - regioselectivity - ring-opening

References and Notes

1 Schöllkopf U. Angew. Chem., Int. Ed. Engl. 1968, 7: 590

Google Scholar
2 Lecornué F. Ollivier J. Chem. Commun. 2003, 584

Crossref Google Scholar
3a Kulinkovich O. Russ. Chem. Bull., Int. Ed. 2004, 53: 1065

Crossref Google Scholar
3b Kulinkovich O. Eur. J. Org. Chem. 2004, 4517

Crossref Google Scholar
4 Sylvestre I. Ollivier J. Salaün J. Tetrahedron Lett. 2001, 4991

Crossref Google Scholar
6 Ngadjui B. Tamboue H. Ayafor JF. Connolly J. Phytochemistry 1995, 39: 1249

Crossref Google Scholar
7a Kato T. Ishii H. Kawai K. Sawa Y. Chem. Pharm. Bull. 1984, 32: 2279

Crossref Google Scholar
7b Kuroda S. Akahane A. Itani H. Nishimura S. Durhin K. Tenda Y. Sakane K. Bioorg. Med. Chem. 2000, 8: 55

Crossref Google Scholar
9 Oshima M. Yamayaki H. Shimizu I. Nisar M. Tsuji J. J. Am. Chem. Soc. 1989, 111: 6280

Crossref Google Scholar
12a Davidson ER. Gajewski JJ. Shook CA. Cohen T. J. Am. Chem. Soc. 1995, 117: 8495

Crossref Google Scholar
12b Shook CA. Romberger ML. Jung S.-H. Xiao M. Sherbine JP. Zhang B. Lin F.-T. Cohen T. J. Am. Chem. Soc. 1993, 115: 10754 ; and references cited therein

Crossref Google Scholar
12c McCullough DW. Cohen T. Tetrahedron Lett. 1988, 29: 27

Crossref Google Scholar
12d Gajewski JJ. Chou SK. J. Am. Chem. Soc. 1977, 99: 5696

Crossref Google Scholar

5

6-Azido-1-vinylcyclohex-1-ene ( 15)
¹H NMR (250 MHz, CDCl₃): δ = 6.33 (dd, J = 17.7, 10.9 Hz, 1 H), 6.06 (t, J = 3.9 Hz, 1 H), 5.30 (d, J = 17.7 Hz, 1 H), 5.08 (d, J = 10.9 Hz, 1 H), 4.12 (br s, 1 H), 2.32-2.00 (m, 3 H), 1.81-1.65 (m, 3 H). ¹³C NMR (63 MHz, CDCl₃): δ = 137.4, 134.2, 132.8, 111.8, 53.9, 29.0, 25.4, 17.4. IR (neat): 2943, 2100, 1643 cm^-1. MS (EI): m/z (%) = 149 (4) [M⁺], 120 (31), 93 (69), 91 (66), 79 (100), 77 (35). HRMS: m/z calcd for C₈H₁₁N₃: 149.0952; found; 149.0950.

8

2-Vinylcyclohex-2-en-1-yl formate ( 16)
¹H NMR (250 MHz, CDCl₃): δ = 8.09 (s, 1 H), 6.22 (dd, J = 17.5, 11.0 Hz, 1 H), 6.08 (t, J = 5.4 Hz, 1 H), 5.81 (m, 1 H), 5.09 (d, J = 17.5 Hz, 1 H), 4.98 (d, J = 11.0 Hz, 1 H), 2.35-1.80 (m, 3 H), 1.80-1.60 (m, 3 H). ¹³C NMR (90 MHz, CDCl₃): δ = 160.6, 136.8, 135.1, 133.4, 111.5, 64.8, 28.5, 25.5, 17.0. IR (neat): 2945, 1718, 1647 cm^-1. MS (EI): m/z (%) = 106 (95), 91 (100), 79 (35), 78 (45). MS (CI, NH₃): m/z (%) = 170 (100) [M⁺ + 18]. HRMS (ES⁺):
m/z calcd for C₁₅H₂₂O₄Na: 289.1410; found: 289.1416.

10

Diethyl (2-Vinylcyclohex-2-en-1-yl)malonate ( 18)
¹H NMR (360 MHz, CDCl₃): δ = 6.21 (dd, J = 17.6, 11.2 Hz, 1 H), 5.87 (t, J = 4.0 Hz, 1 H), 5.11 (d, J = 17.6 Hz, 1 H), 4.91 (d, J = 11.2 Hz, 1 H), 4.19 (q, J = 7.2 Hz, 2 H), 4.09 (q, J = 7.2 Hz, 2 H), 3.62 (d, J = 7.9 Hz, 1 H), 3.31 (m, 1 H), 2.25-2.10 (m, 2 H), 1.90-1.65 (m, 4 H), 1.28 (t, J = 7.2 Hz, 3 H), 1.24 (q, J = 7.2 Hz, 3 H). ¹³C NMR (63 MHz, CDCl₃): δ = 159.6, 138.6, 131.1, 114.3, 61.3, 61.1, 55.0, 54.8, 33.0, 25.7, 25.2, 18.0, 14.1, 13.9. IR (neat): 2936, 1732, 1641 cm^-1. MS (EI): m/z (%) = 175 (20), 161 (67), 160 (78), 133 (44), 119 (20), 115 (24), 106 (100), 91 (93), 79 (25), 78 (34). MS (CI, NH₃): m/z (%) = 267 (100) [M⁺ + 1], 284 (52) [M⁺ + 18]. HRMS (ES⁺): m/z calcd for C₁₅H₂₂O₄Na: 289.1417; found: 289.1416.

11

Diethyl (2-Bicyclo[3.1.0]hex-6-ylideneethyl)malonate ( 19)
¹H NMR (360 MHz, CDCl₃): δ = 5.70 (t, J = 6.6 Hz, 1 H), 4.18 (q, J = 7.2 Hz, 4 H), 3.46 (t, J = 7.5 Hz, 1 H), 2.71 (dd, J = 7.2, 6.6 Hz, 2 H), 1.92-1.65 (m, 8 H), 1.28 (t, J = 7.1 Hz, 3 H), 1.26 (t, J = 7.1 Hz, 3 H). ¹³C NMR (63 MHz, CDCl₃): δ = 173.0, 132.9, 115.2, 61.3, 52.0, 31.0, 29.6, 29.4, 21.2, 20.7, 20.5, 14.0. IR (neat): 2938, 2863, 1750, 1733 cm^-1. MS (EI): m/z (%) = 175 (37), 161 (20), 147 (37), 119 (100), 118 (44), 117 (27), 106 (51), 105 (20), 101 (33), 92 (27), 91 (81), 79 (31). MS (CI, NH₃): m/z (%) = 267 (67) [M⁺ + 1], 284 (100) [M⁺ + 18]. HRMS (ES⁺): m/z calcd for C₁₅H₂₂O₄Na: 289.1417; found: 289.1415.

13

N -(2{(1 R ,5 S )-Bicyclo[3.1.0]hex-6-ylidene}ethyl)-4-methyl- N -[(1 R )-1-phenylethyl] Benzenesulfonamide ( 21)
¹H NMR (250 MHz, CDCl₃): δ = 7.73 (d, J = 7.0 Hz, 4 H), 7.35-7.20 (m, 14 H), 5.52 (t, J = 6.5 Hz, 1 H, minor), 5.48 (t, J = 6.5 Hz, 1 H, major), 5.26 (q, J = 7.0 Hz, 1 H, major), 5.21 (q, J = 7.0 Hz, 1 H, minor), 3.90 (t, J = 6.5 Hz, 1 H, minor), 3.85 (t, J = 6.5 Hz, 1 H, major), 3.73 (d, J = 6.5 Hz, 1 H, major), 3.68 (d, J = 6.5 Hz, 1 H, minor), 2.45 (s, 6 H), 1.80-1.60 (m, 16 H), 1.49 (d, J = 7.0 Hz, 3 H, minor), 1.47 (d, J = 7.0 Hz, 3 H, major). ¹³C NMR (63 MHz, CDCl₃): δ = 142.8, 140.3 (major), 140.2 (minor), 138.8 (major), 138.6 (minor), 136.8, 133.1, 131.9, 129.5, 129.2, 128.1, 128.0, 127.7, 127.5, 127.3, 127.1, 117.3 (major), 117.2 (minor), 55.5 (minor), 55.3 (major), 45.6 (minor), 45.3 (major), 29.5 (major), 29.3 (minor), 21.5 (minor), 21.3 (major), 20.9, 20.5, 17.6 (minor), 17.1 (major). IR (neat): 2939, 2863, 1599 cm^-1. MS (EI): m/z (%) = 381 (3.4) [M⁺], 276 (20), 207 (100), 155 (21), 120 (23), 105(69), 91 (33), 79 (20). HRMS: m/z calcd for C₂₃H₂₇NO₂S: 381.1757; found: 381.1752.