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D. A.


Carbocations: Stability & Structure

Chem 206

Chemistry 206
Advanced Organic Chemistry

Olah, G. A. (2001). “100 Years
of Carbocations and their
Significance in Chemistry.” J.
Org. Chem. 2001, 66, 59445957. (handout)
Walling, C. (1983). “An Innocent
Bystander Looks at the 2-Norbornyl
Acc. Chem. Res. 1983, 16, 448.


Carbocation Stabilization


Carbocation Structures by X-ray Crystallography


Vinyl & Allyl Carbonium Ions

Reading Assignment for this Lecture:
Carey & Sundberg, Advanced Organic Chemistry, 4th Ed. Part A
Chapter 5, "Nucleophilic Substitution", 263-350 .
Birladeanu, L. (2000). "The Story of the Wagner-Meerwein Rearrangement.”
J. Chem. Ed. 2000, 77, 858. (handout)

March, Advanced Organic
Chemistry, 4th Ed. Chapter 5,
Lowery & Richardson, Mech.
& Theory in Org, Chem., 3rd Ed.
pp 383-412.

Laube (1995). “X-Ray Crystal
Structures of Carbocations Stabilized
by Bridging or Hyperconjugation.” Acc.
Chem. Res.1995, 28,: 399 (electronic

Arnett, Hoeflich, Schriver in
Reactive Intermediates Vol 3,
Wiley, 1985, Chapter 5, p 189.

Lecture Number 33

Introduction to Carbonium Ions

Other Relevant

D. A. Evans
11, 2006


Saunders, M. and H. A.
Jimenez-Vazquez (1991).
“Recent studies of
carbocations.” Chem. Rev.
91: 375.

Stang, P. J. (1978). “Vinyl
Triflate Chemistry:
Unsaturated Cations and
Carbenes.” Acc. Chem. Res.
11: 107.
Olah, G. A. and G. Rasul (1997).
“Chemistry in superacids .26. From
Kekule's tetravalent methane to five-,
six- and seven-coordinate protonated
methanes.” Acc. Chem. Res. 30(6):
Olah, G. A. (1995). “My search for
carbocations and their role in
chemistry (Nobel lecture).”
Angew. Chem., Int. Ed. Engl. 34,

Problem 17: The reaction illustrated below was recently reported by Snider and co-workers (Org.
Lett. 2001, 123, 569-572). Provide a mechanism for this transformation. Where stereochemical
issues are present, provide clear three dimensional drawings to support your answer.

CH2Cl2, 0 °C






Carey & Sundberg-A, p 337: Provide
mechanisms for the following







C .



Evans Carbocation Generation & Stability Chem 206 .M. D. Shair.

A.75 2 – 13. A. p 277 Table: pKR+ values of some selected carbenium RCX + R : A r yl + o t h e r c h a r g e s t a b ili zi n g su bst itu ent s X: SO 4 2- . . X: F. SnCl4.0 CHPh CH2 Fe 0.77 Carbocation Generation Hydride abstraction from neutral precursors R3C H + Lewis-Acid H R3C H = H H H RS RS RC + 3 LA–X Acidic dehydratization of secondary and tertiary alcohols Lewis-Acid: Ph3C BF4. 5. SbF BF3Br. OR Carey & Sundberg. FeCl 3.4 H7 C3 + HC 7 3 7.3 CHPh R Cr(CO) –10. salts LA LA: Ag . PCl5. FS O3 - . AlCl3. CF 3S O3 - From neutral precursors via heterolytic dissociation .4 Co2 3 –7. POCl3 . Cl O4 - .Removal of an energy-poor anion from a neutral precursor via Lewis Acids Carbocation Stability: The pKR+ value + R + H2O Definition: ROH + H a K R+ = ROH aR+  +  aH+ a 3 a = activity H2O pKR+ = – log KR+ PCl5 (4-MeO-C6H4)3C 0. ZnCl2. Cl.63 Fe (3-Cl-C6H4)3C – 11.82 Ph3C – 6.. SbCl5. pp 276- 4.2 C3H7 most stable Carey & Sundberg. PCl3.40 Ph 0. I.. BF3.

First step in SN1 or E1 reactions R3C solvent R3C X + X Ability of X to function as a leaving group: + -N > -OSO R' > -OPO(OR') 2 > -I ! -Br > Cl > OH 2 2 Addition of electrophiles to !-systems R R R R R R H H R R R H R H R R Problem 897: Provide a Mechanism of this transformation H2SO4 HC C CH2OH Br .(solvolysis) .

B. A. Breit Carbocation Stabilization Through Hyperconjugation R H C H H C R H C H C H H ✁ FMO Description Take linear combination of  C–R (filled) and C pz-orbital (empty): E ∀ C–R C  C–R ∀ C–R H H C H  C–R Syn-planar orientation between interacting orbitals H Chem 206 . Evans.Carbocations: Structure D.

Scheidt Me Me F Me H Me Carbonium Ion X-ray Structures: Bridged Carbocations Me + 2 SbF5 [F Sb–F–SbF ] 5 Me H Me Me T. 560 5 – Chem 206 . Chem. Laube. Ed. Angew. 26. A. K.D. Int. Evans. 1987.

495 Å 2.739 Å** 1.467 Å .Ph Ph Cl C + Me Me AgSbF6 Me Me F Sb 5 F SbF – 5 1.092 Å 1.

467 Å 1.442 Å **One of the longest documented C–C bond lengths.855 Å 1.50 3Å .+ 1. C C hyperconjugation no bridging 1.

111. Laube. JACS 1989. 9224 .T.

508 1. K.D. 4 Chem 206 . Scheidt Carbonium Ion X-ray Structures: A Summary 66 Å 1.442 Å 1.446 Å + 1.43 9Å Å 1. 34 2 Å 1.421 Å 1 . Evans. A.

432 Å 1.467 Å 1.442 Å 1.371 Å 1.491 Å 1.622 Å 1.513 Å)Ph–C(Me)=CH2 1.725 Å 1.(ref 1.432 Å 1.668 Å Cl + 1.408 Å 2.608 Å Nomenclat ure: classical vs nonclassic 1.503 Å + . 8 5 5 Å 1.422 Å Cl 1.092 Å + 1.495 Å + 1 .621 Å 98.739 Å + 1.467 Å 1.2 ° 1.

551 Å C  CC  C C s y m m e t r i c hyperconju a opengation unsymmetrical l b r i d g i no n trivalentbridging bridging g increasin g nonclass ical characte r cla ssi cal C C C C  C C C  n o n c l a s s i c a l .al 1.

946 Å Si Me Si Si Me . A.221 Å 1.D. EvansChapter 18: Chemistry of Aryl & Vinyl Halides Chem 30 Substitution Reactions Substitution (SN1) R Favorable R Me X H C – –X R Unfavorable Me H X C – –X H2C C R H Sp hybridized Carbon is more electronegative CSp2 Carbonium Ions do exist! Si 1.

B.Me Me CMe3 Normal CC triple bond lengths are ~1. Breit Vinyl & Allyl Carbocations Chem 206 . A.21 Å D. Evans.

affinities (HI) +21 H3 C CH2 276 H +11 H2 C r i n R R R P. HOSolv A s Carbocation Stabilization via delocalization R OTf olv Allyl & Benzyl Carbocations CH 287 (CH3)3C + PhCH3 (CH3) (CH3)3C + PhCH2Cl (CH3 Hydride ion affinities (HI) Ph 298 The ring geometry opposes rehybridization (top) so the vacant . orbital retains sp character. Hydride ion OS allyl cation ✁ Stabilization by Phenylgroups The Benzyl cation is approximately as stable as a tButylcation.S. Stang J. PT II 1977.5 (quite large) indicating strong hyperconjugation and an orientation of the vacant p orbital as shown above.C. 2 g size decreases. Stang J.Vinyl & Phenyl Cations: Highly Unstable Eviden ce sugge sts that vinyl cation s are linear. 1513. the rate of hydrolysis also diminishes. P. Chem Soc. D A secondary kinetic isotope effect R was measured to be KH/KD = 1. 1486. Implying that the formation of the linear vinyl cation is disfavored due to increasing ring strain. effectively prohibiting conjugative stabilization. 93. Additionally. J. J. Am. the empty orbital lies in the nodal plane of the ring. 1971.

80 °C .Hydri de ion affinit ies versu s Rates of Solvo lysis HI -HI Relative Solvolysis rates in 80% EtOH.

A .

D. Evans The Johnson Longifolene Synthesis Chem 206 Ho. 4777 The Cationic Cascade Route to Longifolene The plan ( According to Volkman): H Me Me HO Me Me Me Me Me W. Tantillo. JACS 1975. . JOC 2005. Johnson. 97. Herein we revisit the key polycyclization step of this synthesis using hybrid Hartree-Fock/density functional theory calculations and validate the feasibility of Johnson!s proposed mechanism. 51395143 Volkman. 70. We also explore perturbations to the 3-center 2 electron bonding array in a key intermediate that result from changing the polycyclic framework in which it is embedded. Johnson!s total synthesis of the sesquiterpenoid longifolene is a classic example of the power of cationic polycyclizations for constructing complex molecular architectures. Andrews. A. S. Nouri.

75% CH2 TFA. . K2CO3 longfifolene Me Me HO ZnBr2 NaBH3CN 94% HO Me H CH2 Me steps ZnBr2 longfifolene Me Me Me Me H Me Me Me Me H Me Me Me Me H Me Me FIGURE 1. and CPCM-B3LYP/631G(d) energies in water underlined). B3LYP/6-31G(d) free energies at 0 °C in bold. Relative energies (kcal/mol) of stationary points for the mechanism shown in Scheme 2 (B3LYP/631G(d) zero-point corrected energies in italics.

6 and 3. slide 5-05 for discussion of Walsh orbitals Me OTs Me A rotational barrier of about 13. B.D. Breit Cyclopropyl-carbinyl & Bridgehead Carbocations Carbocation Stabilization via Cyclopropylgroups Chem 206 24 ° Solvolysis rates represent the extend of that cyclopropyl orbital overlap contributing to the stabiliziation of the carbenium ion which is involved as a reactive intermediate: O T s C See Lecture 5. Evans.2 ppm H X-ray Structures support this orientation 1. A. p 286 Bridgehead Carbocation s 1.541 Å Me 1.222 Å R krel = 10 1.444 Å 1 1.534 Å TsO 10-7 .409 Å Me OTs Me 1.302 Å Mek rel =1 OTs O 1.7 kcal/mol is observed in following example: Cl NMR in super acids Me (CH3) = 2.478 Å 1.464 Å 1.517 Å 1.474 Å 6 Carey–A.

Systems with the greatest strain increase upon passing from ground state to transition state react slowest.Bridgehead carbocations are highly disfavored due to a strain increase in achieving planarity. –TsO why so reactive? TsO R. F. JACS 1986. 1692 . Childs. 108.

43 Å) but shorter than the sum of the van der Waals radii (3.483 Å 2. WileyCompounds "Ch VGH.45 2Å For a recent monograph on see emistry of Hypervalent hypervalent : Compounds". J. 1999 . 121.Tedrow A Stable Hypervalent Carbon Compound ? Chem 206 "The Synthesis and Isolation of Stable Hypervalent Carbon Compound (10-C-5) Bearing a 1. K. Akiba. Evans." 2.428 Å 2.8-Dimethoxyanthrecene Ligand" Akibe. JACS 1999. 10644-10645 Me MeO CO Me OMe 2 + OMe Me OMe + – Me3O BF4 O C O B F 2 – 7 "The relevant C–O distances are longer than a covalent C–O bond (1.D. A.452 Å 2.428 Å + 1. et al.25 Å).